Methods to produce molecular sieves with LTA topology and compositions derived therefrom

ABSTRACT

The present disclosure is directed to processing for preparing crystalline pure-silica and heteroatom-substituted LTA frameworks in fluoride media using a simple organic structure-directing agent (OSDA), having a structure of Formula (I): 
                         
where substituents R 1  to R 9  are defined herein. Aluminosilicate LTA is an active catalyst for the methanol to olefins reaction with higher product selectivities to butenes as well as C5 and C6 products than the commercialized catalysts. Titanosilicate LTA is an active catalyst for the epoxidation of allyl alcohol using aqueous H 2 O 2 .

CROSS REFERENCE TO RELATED APPLICATIONS

This applications claims priority to U.S. Patent Application Ser. Nos.62/131,116 filed Mar. 10, 2015 and 62/204,876, filed Aug. 13, 2015, thecontents of which are incorporated by reference herein in theirentireties for all purposes.

TECHNICAL FIELD

The present disclosure is directed to producing molecular sieves withLTA topology using organic structure directing agents (OSDAs), and thecompositions and structures resulting from these methods. The methodsproduce and the compositions comprising pure silicate and substitutedsilicate (e.g., aluminosilicate, germanosilicate, and titanosilicate)LTA products.

BACKGROUND

Microporous materials are crystalline solids formed fromthree-dimensional networks of oxide tetrahedra that contain pores (lessthan 2 nm) and cages that allow for shape-selective ion exchange,separations, and catalysis. These materials often exhibit robusthydrothermal stability that allows their application under demandingprocess conditions such as fluidized catalytic cracking, exhaust gasemissions and treatment of toxic waste. Over 200 different microporousmaterial frameworks have been identified, but of these less than 20 havebeen commercialized, and the market is dominated by only a fewframeworks. Despite this seeming barrier to market entry, the demand toinnovate in these materials remains high as there is often only a singleframework and composition that deliver optimal performance in a givenapplication. In recent years, microporous materials with pore diameterslimited by 8-membered rings have received increased attention as theydemonstrate good activity and hydrothermal stability for high demandapplications such as the methanol-to-olefins (MTO) reaction (SAPO-34)and the reduction of NO_(X) in emissions (SSZ-13).

Zeolite A (Linde Type A, framework code LTA) is one of the most usedzeolites in separations, adsorption, and ion exchange. This structurecontains large spherical cages (diameter ˜11.4 Å) that are connected inthree dimensions by small 8-membered ring (8MR) windows with a diameterof 4.1 Å. LTA is normally synthesized in hydroxide media in the presenceof sodium with Si/Al ˜1. By changing the cation, the limiting diameterof the 8MR windows can be tuned, creating the highly used series ofadsorbents 3A (potassium form, 2.9 Å diameter), 4A (sodium form, 3.8 Ådiameter) and 5A (calcium form, 4.4 Å diameter) that are used toselectively remove species such as water, NH₃, SO₂, CO₂, H₂S, C₂H₄,C₂H₆, C₃H₆ and other n-paraffins from gases and liquids. While LTA isused in vast quantities for the aforementioned applications, the lowframework Si/Al ratio and subsequent poor hydrothermal stability limitsits use under more demanding process conditions that are commonly foundin catalytic applications. Strategies have been developed to increasethe Si/Al up to 5.5 in hydroxide media using combinations of organicstructure directing agents (OSDAs), and this material has been shown tobe active for the MTO reaction.

Pure-silica LTA (ITQ-29) was first reported in 2004 and was synthesizedin fluoride media using a combination of methylated julolidine(4-methyl-2,3,6,7-tetrahydro-1H,5H-pyrido[3.2.1] quinolinium hydroxide(see FIG. 1(A))) and tetramethylammonium (TMA). Pure silica LTA showedan outstanding hydrothermal stability, and aluminum could also beintroduced into the framework, making a material that showed activityfor cracking as well as MTO. Pure-silica LTA has received considerableattention, especially for use in separations and as a membrane, sinceits hydrophobicity and small pore size show good discrimination forsmall molecules; it has also been studied as a low dielectric material.A method to synthesize germanosilicate LTA using a large polycycliccrown ether with the trade name Kryptofix 222 (see FIG. 1(B)) has beendemonstrated. The material has 8MR openings that have 4.1 Å diameter anda spherical 3D network of 11.4 Å cavities. More recently, a method ofpreparing molecular sieves with LTA topologies have used triquaternaryOSDAs, such as shown in FIG. 1(C).

In recent years there has been considerable interest in 8MR systems forcatalysis and separations. Some of the most promising catalyticapplications are the methanol to olefins (MTO) conversion and deNOx.Other 8MR materials of interest are LEV, CHA and AFX. It has been foundthat the cage size and connectivity are critical in determining theproduct distribution for these reactions in 8MR systems. LTA possesses aunique cage size and will likely exhibit unique catalytic performance.However, in order to produce an aluminosilicate material with thenecessary silicon to aluminum ratio for the MTO reaction, a complicatedOSDA is required, as shown in FIGS. 1(A-C). The nature of the organicmakes it unlikely this material could be used in commercial production.The SDA-free syntheses of LTA can only be made at low Si/Al ratios andare less than optimal for catalysis.

The present invention is directed to addressing at least some of theshortcomings of the existing art.

SUMMARY

The present invention is directed to the use of benzyl-3H-imidazol-1-iumcations, one example being shown in FIG. 2, to prepare zeolites havingLTA topologies, and the novel materials derived from these processes.

The disclosure provided certain embodiments directed to processes ofmaking silicate compositions of a LTA topology, each process comprisinghydrothermally treating an aqueous composition comprising:

-   -   (a) a source of a silicon oxide;    -   (b) an optional source of aluminum oxide;    -   (c) an optional source of germanium oxide;    -   (d) an optional source of titanium oxide;    -   (e) an optional source of one or more of boron oxide, gallium        oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,        indium oxide, vanadium oxide, zinc oxide, zirconium oxide, or        combination or mixture thereof;    -   (f) a mineralizing agent; and    -   (g) an organic structure directing agent (OSDA) comprising a        substituted benzyl-3H-imidazol-1-ium cation of Formula (I):

under conditions effective to crystallize a crystalline microporoussolid of LTA topology;

-   -   wherein    -   R¹, R², and R⁷ are independently C₁₋₃ alkyl;    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl;        and        the substituted benzyl-3H-imidazol-1-ium cation has an        associated bromide, chloride, fluoride, iodide, nitrate, or        hydroxide anion. In certain aspects of the disclosure, the OSDA        may comprise additional organic materials known to crystalline        microporous solid of LTA topology. In other aspects of the        disclosure, the aqueous composition comprises seeds having LTA        topology.

The nature of the sources of the various oxides and their ratio ranges,the nature of the mineralizing agent, and the hydrothermal heatingconditions are also disclosed as separate embodiments. Depending on thespecific sources of metal or metalloid oxides, the processes can be usedto prepare pure- and optionally substituted silicates, aluminosilicates,germanosilicates, and/or titanosilicates having an LTA topology.

Certain subset embodiments of the OSDAs are also disclosed. In one suchembodiment, the OSDA comprises a2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium cation of Formula(IB):

In other embodiments, the processes further comprise isolating thecrystalline microporous silicate solids of LTA topology and in somecases, further processing these isolated crystalline solids. In severalcases, these processes include process steps to remove at least aportion, and preferably substantially all, of the OSDA occluded in thepores of the isolated solids. In some embodiments, this furtherprocessing is done in the presence of an alkali, alkaline earth,transition metal, rare earth metal, ammonium or alkylammonium salts(anions including halide, preferable chloride, nitrate, sulfate,phosphate, carboxylate, or mixtures thereof) to form a dehydrated or anOSDA-depleted product. In other aspects, these salts are added in aseparate step from the removal of the OSDA.

Associated to these processes are the analogous compositions used in theprocesses. These embodiments of the compositions also specificallydefined on terms of the nature of the OSDA, the ratios of the variouscomponents, and the processing conditions. Still other embodimentsprovide for crystalline microporous solids having pores at least some ofwhich are occluded with the various 1-benzyl-3-alkyl-3H-imidazol-1-iumOSDAs described herein. Other embodiments include those where the poresare substantially or completely OSDA-depleted.

The products of the hydrothermal treating may be isolated and subjectedto one or more of further processing conditions. Such treatmentsinclude:

-   -   (a) contacting the isolated crystalline microporous solid with        ozone or other oxidizing agent at a temperature in a range of        100° C. to 200° C.; and    -   (b) heating the isolated crystalline microporous solid at a        temperature in a range of from about 200° C. to about 600° C. in        the presence of an alkali, alkaline earth, transition metal,        rare earth metal, ammonium or alkylammonium salts;        in each case for a time sufficient to form a dehydrated or an        OSDA-depleted crystalline microporous product. Certain        sub-embodiments describe specific aspects of these treatments.

These dehydrated or OSDA-depleted crystalline microporous products maybe further treated with an aqueous ammonium or metal cation salt and/orwith at least one type of transition metal or transition metal oxide.

Various embodiments disclose the compositions prepared by any one of theprocesses embodiments. These include compositions which may be describedas:

-   -   (a) compositions comprising the aqueous compositions used in the        hydrothermal treatments together with a compositionally        consistent crystalline microporous aluminosilicate product, the        compositionally consistent crystalline microporous products        containing the OSDA used in their preparation occluded in their        pores;    -   (b) the isolated crystalline microporous products which contain        the 1-benzyl-3-alkyl-3H-imidazol-1-ium cations of Formula (I)        occluded in their pores; and    -   (c) the crystalline microporous products which have been        dehydrated or from which the OSDAs have been substantially        depleted from their pores and/or which have been post-treated to        add salts, metals, or metal oxides into the pores of the        crystalline microporous products.

In other embodiments, the crystalline microporous solids are describedin terms of certain physical characteristics of the aluminosilicatesolids, for example with respect to XRD patterns, ²⁹Si MAS NMR spectra,²⁷Al MAS NMR spectra, N₂ or argon physisorption isotherms, andthermogravimetric analysis (TGA) data.

Still other embodiments include those in which the disclosedcompositions, either as simple or chemically modified silicateframeworks, are used in an array of catalytic or separation processes.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods of making and methods of using,processes, devices, and systems disclosed. In addition, the drawings arenot necessarily drawn to scale. In the drawings:

FIGS. 1(A-C) show previously the only known OSDAs for syntheticpreparation of LTA-type materials: OSDA for the preparation of ITQ-29(FIG. 1(A)) and OSDA for the preparation of germanosilicate LTA (FIG.1(B)) and OSDA for the preparation of molecular sieves with LTAtopologies (FIG. 1(C)).

FIG. 2 shows general flow summary for the disclosed systems.

FIG. 3 shows synthetic scheme for the preparation of1,2-dimethyl-3-(4-methyl-benzyl)-1H-imidazol-3-ium cations (chloride andhydroxide salts).

FIG. 4 shows an SEM image of an exemplary pure-silica LTA. Bar=30microns.

FIG. 5 shows powder X-ray diffraction patterns of as-made (lower) andcalcined (upper) pure-silica LTA. The inset image is of the calcinedmaterial with the intensity increased to show the reflections moreclearly.

FIG. 6 shows the OSDA used to make pure-silica LTA along with the liquidcarbon NMR (lower) and the ¹³C CPMAS NMR of as-made pure silica LTA. Therelative sharpness of the TMA resonance (marked by arrow) is narrow dueto its fast rotation within the pores.

FIGS. 7(A-B) show solid state ²⁹Si CPMAS NMR spectra of an as-made puresilica LTA (FIG. 7(A)) and a calcined pure silica LTA (FIG. 7(B)).

FIG. 8 shows an ¹⁹F NMR of as-made silica LTA. Spinning sidebands aremarked with *.

FIG. 9(A) shows a nitrogen adsorption isotherm data derived fromcalcined pure-silica LTA (t-plot micropore volume of 0.25 cc/g); FIG.9(B) shows an Argon adsorption isotherm of calcined pure-silica LTA; andFIG. 9(C) shows a log plot argon adsorption isotherm of calcinedpure-silica LTA.

FIG. 10 shows a TGA analysis of as-made pure-silica LTA made with andwithout TMA.

FIG. 11 shows an SEM image of aluminosilicate LTA produced in fluoridemediated reactions. Bar=30 microns.

FIG. 12 shows PXRD traces of an aluminosilicate LTA, as-made (lowertrace) and calcined (upper trace).

FIGS. 13(A-C) shows show solid state ²⁷Al NMR of aluminosilicate LTAs:

-   -   an as-made sample, from gel Si/Al=30.8 (FIG. 13(A)); a second        as-made sample, from gel Si/Al=20 (FIG. 13(B)); and calcined        sample of gel having Si/Al=20 (FIG. 13(C)). Spinning sidebands        are marked with *.

FIGS. 14(A-B) show PXRD traces for germanosilicates prepared from gelswherein the molar ratio of Si:Ge was 16:1 (FIG. 14(A)) and 8:1(FIG.14(B)).

FIG. 15 shows a DR-UV spectrum of titanosilicate LTA

FIG. 16 shows MTO reaction data for calcined aluminosilicate LTA.

FIGS. 17(A-D) show MTO reaction data for calcined aluminosilicate LTA,in samples where Si/Al=12 (FIG. 17(A)); Si/Al=33 (FIG. 17(B)); Si/Al=38(FIG. 17(C)); and Si/Al=42 (FIG. 17(D)).

FIGS. 18(A-D) show MTO reaction data for samples of structure SSZ-13(Si/Al=19)(FIG. 18 (A)); SAPO-34(FIG. 18 (B)); RTH (Si/Al=17) (FIG. 18(C)); and RTH (Si/Al=29) (FIG. 18 (D)).

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention is directed to methods of producing crystallinepure-silica and heteroatom LTA frameworks, under conditions typical forfluoride-mediated microporous materials syntheses. Embodiments of thedisclosure include methods of making and using such crystallinematerials and compositions comprising these structures, both as-made andas further processed. These LTA materials, particularly thealuminosilicate LTA material is shown to be an active catalyst for theMTO reaction and shows interesting product selectivities compared toother 8MR materials. Germanosilicates and titanosilicate, the latterbeing a Lewis acidic LTA, can also be prepared using this method anditself may have possible applications where the 8MR ring and large,spherical cage size and may show advantages over larger pore materials.

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, processes, conditions or parameters described or shown herein,and that the terminology used herein is for the purpose of describingparticular embodiments by way of example only and is not intended to belimiting of any claimed invention. Similarly, unless specificallyotherwise stated, any description as to a possible mechanism or mode ofaction or reason for improvement is meant to be illustrative only, andthe invention herein is not to be constrained by the correctness orincorrectness of any such suggested mechanism or mode of action orreason for improvement. Throughout this specification, claims, anddrawings, it is recognized that the descriptions refer to compositionsand processes of making and using said compositions. That is, where thedisclosure describes or claims a feature or embodiment associated with acomposition or a method of making or using a composition, it isappreciated that such a description or claim is intended to extend thesefeatures or embodiment to embodiments in each of these contexts (i.e.,compositions, methods of making, and methods of using).

TERMS

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. Similarly, unless otherwise specified, a given value carrieswith it the term “about” as an independent embodiment. In general, useof the term “about” indicates approximations that can vary depending onthe desired properties sought to be obtained by the disclosed subjectmatter and is to be interpreted in the specific context in which it isused, based on its function. The person skilled in the art will be ableto interpret this as a matter of routine. In some cases, the number ofsignificant figures used for a particular value may be one non-limitingmethod of determining the extent of the word “about.” In other cases,the gradations used in a series of values may be used to determine theintended range available to the term “about” for each value. Wherepresent, all ranges are inclusive and combinable. That is, references tovalues stated in ranges include every value within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of,” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method or process steps; (ii) “consisting of” excludes anyelement, step, or ingredient not specified in the claim; and (iii)“consisting essentially of” limits the scope of a claim to the specifiedmaterials or steps “and those that do not materially affect the basicand novel characteristic(s)” of the claimed invention. Embodimentsdescribed in terms of the phrase “comprising” (or its equivalents), alsoprovide, as embodiments, those which are independently described interms of “consisting of” and “consisting essentially of” For thoseembodiments provided in terms of “consisting essentially of” the basicand novel characteristic(s) of a process is the ability to provide thenamed LTA compositions using the named OSDAs under conditions favoringthe stable formation of the LTAS compositions, without the necessaryneed for other ingredients, even if other such components are present.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C.”

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are described herein.

Unless otherwise stated, ratios or percentages are intended to refer tomole percent or atom percent, as appropriate.

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

“Lower alcohols” or lower alkanes refer to alcohols or alkanes,respectively, having 1-10 carbons, linear or branched, preferably 1-6carbon atoms and preferably linear. Methanol, ethanol, propanol,butanol, pentanol, and hexanol are examples of lower alcohols. Methane,ethane, propane, butane, pentane, and hexane are examples of loweralkanes.

The terms “oxygenated hydrocarbons” or “oxygenates” as known in the artof hydrocarbon processing to refer to components which include alcohols,aldehydes, carboxylic acids, ethers, and/or ketones which are known tobe present in hydrocarbon streams or derived from biomass streams othersources (e.g. ethanol from fermenting sugar).

The terms “separating” or “separated” carry their ordinary meaning aswould be understood by the skilled artisan, insofar as they connotephysically partitioning or isolating the product material from otherstarting materials or co-products or side-products (impurities)associated with the reaction conditions yielding the material. As such,it infers that the skilled artisan at least recognizes the existence ofthe product and takes specific action to separate or isolate it fromstarting materials and/or side- or byproducts. Absolute purity is notrequired, though it is preferred.

Unless otherwise indicated, the term “isolated” means physicallyseparated from the other components so as to be free of at leastsolvents or other impurities, such as starting materials, co-products,or byproducts. In some embodiments, the isolated crystalline materials,for example, may be considered isolated when separated from the reactionmixture giving rise to their preparation, from mixed phase co-products,or both. In some of these embodiments, for example, pure silicates,aluminosilicates, germanosilicates, or titanosilicates (or structurescontaining incorporated OSDAs) can be made directly from the describedmethods. In some cases, it may not be possible to separate crystallinephases from one another, in which case, the term “isolated” can refer toseparation from their source compositions.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesseparate embodiments where the circumstance occurs and embodiments whereit does not. For example, the phrase “optionally substituted” means thata non-hydrogen substituent may or may not be present on a given atom,and, thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present. Similarly, the phrase “optionally isolated” means thatthe target material may or may not be separated from other materialsused or generated in the method, and, thus, the description includesseparate embodiments where the target material is separated and wherethe target material is not separated, such that subsequence steps areconducted on isolated or in situ generated product.

The terms “method(s)” and “process(es)” are considered interchangeablewithin this disclosure.

As used herein, the term “crystalline microporous solids” or“crystalline microporous silicate or heteroatom-containing silicatesolids,” sometimes referred to as “molecular sieves,” are crystallinestructures having very regular pore structures of molecular dimensions,i.e., under 2 nm. The term “molecular sieve” refers to the ability ofthe material to selectively sort molecules based primarily on a sizeexclusion process. The maximum size of the species that can enter thepores of a crystalline microporous solid is controlled by the dimensionsof the channels. These are conventionally defined by the ring size ofthe aperture, where, for example, the term “8-MR” or “8-membered ring”refers to a closed loop that is typically built from eight tetrahedrallycoordinated silicon, or heteroatoms and 8 oxygen atoms. These rings arenot necessarily symmetrical, due to a variety of effects includingstrain induced by the bonding between units that are needed to producethe overall structure, or coordination of some of the oxygen atoms ofthe rings to cations within the structure.

The term “silicate” refers to any composition including silicate (orsilicon oxide) within its framework. It is a general term encompassing,for example, pure-silica (i.e., absent other detectable metal oxideswithin the framework), aluminosilicate, borosilicate, germanosilicate,or titanosilicate structures. The term “zeolite” refers to analuminosilicate composition that is a member of this family. The term“aluminosilicate” refers to any composition including silicon andaluminum oxides within its framework. In some cases, either of theseoxides may be substituted with other oxides. “Pure aluminosilicates” arethose structures having no detectable other metal oxides in theframework. As long as the framework contains silicon and aluminumoxides, these substituted derivatives fall under the umbrella ofaluminosilicates. Similarly, the term “germanosilicate” refers to anycomposition including silicon and germanium oxides within its framework.Such germanosilicate may be “pure-germanosilicate (i.e., absent otherdetectable metal oxides within the framework) or optionally substituted.Similarly, the term “titanosilicate” refers to any composition includingsilicon and titanium oxides within its framework. Such titanosilicatemay be “pure-titanosilicate (i.e., absent other detectable metal oxideswithin the framework) or optionally substituted. When described as“optionally substituted,” the respective framework may contain aluminum,boron, gallium, germanium, hafnium, iron, tin, titanium, indium,vanadium, zirconium, or other atoms substituted for one or more of theatoms not already contained in the parent framework.

The present disclosure describes and is intended to lay claim to methodsof making crystalline compositions having LTA topologies, thecompositions themselves, and methods of using these crystallinecompositions. The structural features associated with the LTA topologyare well-understood by those skilled in the art and are summarized, forexample, in the Database of Zeolite Structures, maintained by theInternational Zeolite Association (IZA-SC). The most recently availableDatabase at the timing of this disclosure is incorporated by referencefor its descriptions of these topologies. Also as described elsewhere aswell, it should be appreciated that any embodied feature described forone of these categories (i.e., compositions and methods of making orusing) is applicable to all other categories.

Processes of Preparing Crystalline Compositions

Certain embodiments of the present disclosure include process forpreparing crystalline microporous silicate compositions having an LTAtopology, each process comprising hydrothermally treating an aqueouscomposition comprising:

-   -   (a) a source of a silicon oxide;    -   (b) an optional source of aluminum oxide;    -   (c) an optional source of germanium oxide;    -   (d) an optional source of titanium oxide;    -   (e) an optional source of one or more of boron oxide, gallium        oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,        indium oxide, vanadium oxide, zinc oxide, zirconium oxide, or        combination or mixture thereof;    -   (f) a mineralizing agent; and    -   (g) an organic structure directing agent (OSDA) comprising a        substituted benzyl-3H-imidazol-1-ium cation of Formula (I):

under conditions effective to crystallize a crystalline microporoussolid of LTA topology;

-   -   wherein    -   R¹, R², and R⁷ are independently C₁₋₃ alkyl (i.e., methyl,        ethyl, n-propyl, or iso-propyl);    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl.

The counterion to the substituted benzyl-3H-imidazol-1-ium cation inFormula (I) is generally a bromide, chloride, fluoride, iodide, orhydroxide ion, but the OSDA may be added also to the composition as anacetate, nitrate, or sulfate. In some embodiments, the quaternary cationhas an associated fluoride or hydroxide ion, preferably substantiallyfree of other halide counterions. In separate embodiments, theassociated anion is hydroxide.

The process (and associated compositions) may include the use ofsubstituted benzyl-3H-imidazol-1-ium cation of Formula (I), wherein oneor more of R¹, R², and R⁷ are independently methyl or ethyl. In otherembodiments, one or more of R¹, R², and R⁷ are independently methyl. Instill other embodiments, all of R¹, R², and R⁷ are methyl.

Additionally, in some embodiments, one or more of R³, R⁴, R⁵, R⁶, R⁸,and R⁹ are independently H or methyl. In other embodiments, one or moreof R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or methyl. In otherembodiments, all of R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are H. For example, incertain aspects of these embodiments, the OSDA comprises a2,3-dialkyl-1-(4-alkyl-benzyl)-3H-imidazol-1-ium cation of Formula (IA):

The OSDA may also comprise a2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium cation of Formula(IB):

(2,3-Dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium).

In some embodiments, the substituted benzyl-3H-imidazol-1-ium cation canbe used in conjunction with lesser amounts of other OSDAs known toaffect the formation of LTA-type topologies, for example, the structuresshown in FIG. 1(A-C) (i.e., tetra-alkyl, especially tetramethyl,ammonium salts, methylated julolidine, polycyclic crown ethers likeKryptofix 222, or Triquats). In some embodiments, the relative molarratio of these other OSDA (either individually or collectively) to thepresent optionally substituted benzyl-3H-imidazol-1-ium cation is in arange of from 0 to 0.05, from 0.05 to 0.1, from 0.1 to 0.15, from 0.15to 0.2, from 0.2 to 0.25, from 0.25 to 0.3, from 0.3 to 0.35 to 0.4,from 0.4 to 0.45, from 0.45 to 0.5, or a range combining any two or moreof these ranges, for example, from 0 to 0.15.

As described above, the hydrothermal processes for preparing thecrystalline microporous silicate solids of LTA topology requires, interalia: (a) a source of a silicon oxide. This source of silicon oxide maycomprise a silicate, silica hydrogel, silicic acid, fumed silica,colloidal silica, tetra-alkyl orthosilicate, a silica hydroxide orcombination thereof. Sodium silicate or tetraorthosilicates arepreferred sources. The sources of silicon oxide may be amorphous (i.e.,the XRD pattern of the solid showing little or no structure),microcrystalline (i.e., the XRD pattern of the solid showing broadenedreflectance peaks indicative of a small degree of long range order), orcrystalline (i.e., the XRD pattern of the solid showing well defined andsharp reflectance peaks). Any of the silicates (or heretoatomsubstituted silicates) may be of a topology or composition differentthan the topology or composition of the intended product (e.g.,different than the LTA topology eventually prepared and/or isolated). Inother embodiments, the silicate is the same topology or composition asthe topology or composition of the intended product, for example, actingas seeds. For example, the use of LTA silicate seeds has proven to beuseful in the formation of aluminosilicate LTA structures (seeExamples).

Where the aqueous composition is free from any of the optional sourcesof metal oxides, the process yields crystalline microporouspure-silicate materials of LTA topology, the term “pure” reflecting theabsence of all but the inevitable impurities present in the sources ofsilicon oxides. In independent embodiments, the aqueous composition tobe hydrothermally treated (or being hydrothermally treated) compriseseach and every individual or combination optional sources of the metaloxides and the process yields crystalline microporous silicate LTAsolids of the corresponding substituted framework.

Within this general description, the hydrothermal processes forpreparing the crystalline microporous aluminosilicate solids of LTAtopology requires, inter alia: (a) a source of a silicon oxide; and (b)a source of aluminum oxide, the resulting crystalline microporous solidbeing characterized as an aluminosilicate. In some embodiments, thesource of aluminum oxide is or comprises an alkoxide, hydroxide, oroxide of aluminum, a sodium aluminate, an aluminum siloxide, analuminosilicate, or combination thereof. In some embodiments, amesoporous or zeolite aluminosilicate material may be used as a sourceof both aluminum oxide and silicon oxide. For example, FAU type zeolitesserve as useful precursors, for example in structures having Si/Al=2.6.In separate embodiments, the aqueous composition is absent of orcontains any of the optional sources of the metal oxides. Where thecomposition contains only sources of aluminum and silicon oxides, theresulting crystalline material is typically characterized as apure-aluminosilicate solid of LTA topology, again, the term “pure”reflecting the absence of all but the inevitable impurities present inthe sources of aluminum and silicon oxides.

Many of the sources of the various metals or metalloids can bealkoxides. In those cases where the source of metal oxide is an alkoxideof a metal M, for example of formula M(OR)n, where n is the nominalvalence of M, R is one or more alkyl groups of 1-6 carbon atoms,including methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, n-pentyl, isopentyl, hexyl Some of these compounds, forexample Al(OR)₃, can form complicated bridging structures in solution,even before hydrolysis. In independent embodiments, the silicon alkoxideis tetraethyl orthosilicate (TEOS), the aluminum alkoxide is Al(i-OPr)₃,and the source of titanium alkoxide is Ti(O-butoxide)₄. In some cases,where compositionally appropriate, the source of the metal oxides mayalso comprise mixed metal oxides, hydroxides, or alkoxides, for examplealuminosilicate, aluminum siloxide, aluminosilicate, germanosilicates,titanosilicates, etc. In some aspects, when mixed metal oxides are used,mixed oxide sources may be compositionally or topologically differentthan the targeted LTA product topology. In other aspects, the mixedoxide sources may be compositionally or topologically the same as thetargeted LTA product topology, for example if uses as seeds; forexample, where the AlSi-LTA, GeSi-LTA, or TiSi-LTA are seeded withSi-LTA seeds.

In still other embodiments, the aqueous composition comprises, interalia, (a) a source of a silicon oxide; and (c) a source of a germaniumoxide. Where the only sources of metal oxide sources are sources ofsilicon and germanium oxides, the process yields pure germanosilicatesolids of LTA topology, the term “pure” reflecting the absence of allbut the inevitable impurities present in the sources of germanium andsilicon oxides. Other embodiments provide for the presence of one ormore of the sources of optional metal oxides, in which case the presenceof one or more of the optional sources of metal may result incorrespondingly substituted frameworks. Sources of germanium oxide caninclude alkali metal orthogermanates, M₄GeO₄, containing discrete GeO₄⁴⁻ ions, GeO(OH)₃ ⁻, GeO₂(OH)₂ ²⁻, [(Ge(OH)₄)₈(OH)₃]³⁻ or neutralsolutions of germanium dioxide contain Ge(OH)₄, or alkoxide orcarboxylate derivatives thereof.

In a similar fashion, in some embodiments, the aqueous compositioncomprises, inter alia, (d) a source of a titanium oxide, admixed withthe source of silicon oxide. In some of these embodiments, thecomposition further comprises any one or more optional source of theoptional metal oxides. Where the only sources of metal oxide sources aresources of silicon and titanium oxides, the process yields puretitanosilicate solids of LTA topology, the term “pure” reflecting theabsence of all but the inevitable impurities present in the sources oftitanium and silicon oxides. Other embodiments provide for the presenceof one or more of the sources of optional metal oxides, in which casethe presence of one or more of the optional sources of metal may resultin correspondingly substituted frameworks. Sources of titanium oxide caninclude titanium alkoxides, oxides, or hydrated or hydrolyzed hydroxyloxides.

Thus far, the processes (and associated compositions) have beendescribed as in terms of the use or presence of a mineralizing agent. Insome embodiments, the mineralizing agent comprises an aqueous alkalimetal or alkaline earth metal hydroxide, thereby rendering thesecompositions alkaline. In certain aspects of this embodiment, the alkalimetal or alkaline earth metal hydroxide, may include, for example, LiOH,NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂. LiOH,NaOH, or KOH appear to be preferred. In some cases, the pH of the wateris in a range of from 7 to 7.5, from 7.5 to 8, from 8 to 8.5, from 8.5to 9, from 9 to 9.5, from 9.5 to 10, from 10 to 11, from 11 to 12, from12 to 13, from 13 to 14, or a range combining any two or more of theseranges. Under these conditions, the oxide precursors can be expected tobe at least partially hydrated to their hydroxide forms.

In other embodiments, the mineralizing agent is or comprises a source offluoride ion. Aqueous hydrofluoric acid is particularly suitable forthis purpose, whether used as provided, or generated in situ by otherconventional methods. Such sources of HF can include:

-   -   (a) aqueous ammonium hydrogen fluoride (NH₄F.HF);    -   (b) an alkali metal bifluoride salt (i.e., MHF₂, where M⁺ is        Li⁺, Na⁺, or K⁺), or a combination thereof; or    -   (c) at least one fluoride salt, such as an alkali metal,        alkaline earth metal, or ammonium fluoride salt (e.g., LiF, NaF,        KF, CsF, CaF₂, tetraalkyl ammonium fluoride (e.g., tetramethyl        ammonium fluoride)) in the presence of at least one mineral acid        that is stronger than HF (e.g., HCl, HBr, HI, H₃PO₄, HNO₃,        oxalic acid, or H₂SO₄) and can react with fluorides to form HF        in situ; or    -   (d) a combination of two or more of (a)-(c). Volatile sources of        fluoride (e.g., HF, NH₄F, or NH₄F.HF) are preferred.

The processes and compositions may also be defined in terms of theratios of the individual ingredients. In certain embodiments, the molarratio of the OSDA:Si is in a range of from 0.1 to 0.15, from 0.15 to0.2, from 0.2 to 0.25, from 0.25 to 0.3, from 0.3 to 0.35, from 0.35 to0.4, from 0.4 to 0.45, from 0.45 to 0.5, from 0.5 to 0.55, from 0.55 to0.6, from 0.6 to 0.65, from 0.65 to 0.7, from 0.7 to 0.75, from 0.75 to0.8, from 0.8 to 0.85, from 0.85 to 0.9, from 0.9 to 0.95, from 0.95 to1, or a range combining any two or more of these ranges, for examplefrom 0.4 to 0.6 or from 0.4 to 0.75. In this regard, the referenced OSDAis or comprises the substituted benzyl-3H-imidazol-1-ium cation ofFormula (I). In those embodiments, where the substitutedbenzyl-3H-imidazol-1-ium cation is used in complement with the otherOSDAs referenced elsewhere herein, the OSDA:Si ratio refers the totalOSDA content.

In other embodiments, the molar ratio of water:Si is in a range of fromabout 2 to 3, from 3 to 4, from 4 to 5, from 5 to 6, from 6 to 7, from 7to 8, from 8 to 9, from 9 to 10, from 10 to 11, from 11 to 12, from 12to 13, from 13 to 14, from 14 to 15, from 15 to 16, from 16 to 17, from17 to 18, from 18 to 19, from 19 to 20, or a range combining any two ormore of these ranges, for example in a range of from about 2 to about10, from about 4 to 10, or from 4 to 8.

In preparing the aluminosilicates, the molar ratio of Al:Si can be in arange of from 0 to 0.005, from 0.005 to 0.01, from 0.01 to 0.015, from0.015 to 0.02, from 0.02 to 0.025, from 0.025 to 0.3, from 0.03 to 0.035to 0.04, from 0.04 to 0.045, from 0.045 to 0.05, from 0.05 to 0.055,from 0.055 to 0.06, from 0.06 to 0.065, from 0.065 to 0.07, from 0.07 to0.075 to 0.08, from 0.08 to 0.085, from 0.085 to 0.09, from 0.09 to0.095, from 0.095 to 0.1, or a range combining any two or more of theseranges, for example, from 0.01 to 0.05 (molar range of Si:Al from 20 to100)

In preparing the germanosilicates, the molar ratio of Ge:Si can be in arange of from 0 to 1 (Si/Ge=1 to infinity); in some embodiments, themolar ratio of Ge:Si is in a range of from 0 to 0.05, from 0.05 to 0.1,from 0.1 to 0.15, from 0.15 to 0.2, from 0.2 to 0.25, from 0.25 to 0.3,from 0.3 to 0.35, from 0.35 to 0.4, from 0.4 to 0.45, from 0.45 to 0.5,from 0.5 to 0.55, from 0.55 to 0.6, from 0.6 to 0.65, from 0.65 to 0.7,from 0.7 to 0.75, from 0.75 to 0.8, from 0.8 to 0.85, from 0.85 to 0.9,from 0.9 to 0.95, from 0.95 to 1, or a range combining any two or moreof these ranges, for example, from 0.05 to 1 or from 0.05 to 0.5 (molarrange of Si:Ge from 20 to 100)

In preparing the titanosilicates, the molar ratio of Ti:Si can be in arange of from 0 to 0.005, from 0.005 to 0.01, from 0.01 to 0.015, from0.015 to 0.02, from 0.02 to 0.025, from 0.025 to 0.03, from 0.03 to0.035, from 0.035 to 0.04, from 0.04 to 0.045, from 0.045 to 0.05, from0.05 to 0.055, from 0.055 to 0.06, from 0.06 to 0.065, from 0.065 to0.07, from 0.07 to 0.075, from 0.075 to 0.08, from 0.08 to 0.085, from0.085 to 00.9, from 0.09 to 0.095, from 0.095 to 0.1, or a rangecombining any two or more of these ranges, for example, from 0.005 to0.02 (molar range of Si:Ti from 50 to 200).

Where the mineralizing agent is a fluoride source, such as HF, the molarratio of fluoride:Si may be in a range of from about 0.1 to 0.15, from0.15 to 0.2, from 0.2 to 0.25, from 0.25 to 0.3, from 0.3 to 0.35, from0.35 to 0.4, from 0.4 to 0.45, from 0.45 to 0.5, from 0.5 to 0.55, from0.55 to 0.6, from 0.6 to 0.65, from 0.65 to 0.7, from 0.7 to 0.75, or arange combining any two or more of these ranges, for example in a rangeof from about 0.4 to about 0.6.

To this point, the processes have been defined in terms of conditionsunder conditions effective to crystallize a respective crystallinemicroporous solid of LTA topology. In light of the other teachingswithin this disclosure, this is believed to be a sufficient description.But in certain aspects of this, these conditions include treatment ofthe respective hydrothermally treated aqueous composition at atemperature in a range of from 100° C. to 110° C., from 110° C. to 120°C., from 120° C. to 125° C., from 125° C. to 130° C., from 130° C. to135° C., from 135° C. to 140° C., from 140° C. to 145° C., from 145° C.to 150° C., from 150° C. to 155° C., from 155° C. to 160° C., from 160°C. to 165° C., from 165° C. to 170° C., from 170° C. to 175° C., from175° C. to 180° C., from 180° C. to 185° C., from 185° C. to 190° C.,from 190° C. to 195° C., from 195° C. to 200° C., or a range combiningany two or more of these ranges, for example, from 120° C. to 160° C. Inrelated embodiments, the times of this treatment, while dependent on thespecific reaction conditions (e.g., temperatures and concentrations),can range from 3 to 40 days, preferably from 7 to 40 days. These rangesprovide for convenient reaction times, though higher and lowertemperatures and longer or shorter times may also be employed. Thishydrothermal treating is also typically done in a sealed autoclave, atautogenous pressures. Some additional exemplary reaction conditions areprovided in the Examples.

In some embodiments the reaction mixture can be subjected to mildstirring or rolling agitation during crystallization. It will beunderstood by a person skilled in the art that the as producedcrystalline microporous solid s described herein can contain impurities,such as amorphous materials, or materials having framework topologieswhich do not coincide with the targeted or desired molecular sieve.During hydrothermal crystallization, the molecular sieve crystals can beallowed to nucleate spontaneously from the reaction mixture.

As described above, the use of crystals of the molecular sieve as seedmaterial can result in decreasing the time necessary for completecrystallization to occur. In addition, seeding can lead to an increasedpurity of the product obtained by promoting the nucleation and/orformation of the molecular sieve over any undesired phases. When used asseeds, seed crystals are added in an amount between 0.01% and 10% of themass of the total amount of oxide in the reaction mixture. The totalamount of oxide refers to the total mass of oxides in the reactionmixture gel prior to heating, present as the oxides or oxide sources.

In some embodiments, silicate membranes or films can be formed bybringing an optionally porous support (e.g., comprising porous alumina,pretreated silicon wafers, or other organic or inorganic polymer capableof withstanding the hydrothermal treating conditions) in contact withthe aqueous composition to be hydrothermally treated and maintaining thesystem under conditions to nucleate and/or grow a thin continuous filmon the surface and/or in the pores of the support. In some embodiments,pre-nucleated seed crystals of LTA topology are deposited on the support(for example, by dipcoating the support into a suspension of seedcrystals) before contacting with the aqueous compositions. Maintainingthe systems under appropriate hydrothermal conditions provides membranes(as opposed to individual crystals) that are generally highly selectiveand appropriately permeable. Removing the OSDAs after the formation ofthe crystalline membranes or films can be accomplished by any of thepost-treatments described elsewhere herein for these materials.Exemplary parallel systems have been described in H. K. Hunt, et al.,Microporous and Mesoporous Mat'ls., 128 (2010) 12-18 and H. K. Hunt, etal., Microporous and Mesoporous Mat'ls., 130 (2010) 49-55, both of whichare incorporated by reference in their entireties for all purposes.

Once the initially-formed crystalline microporous solids of LTA topologyare prepared (e.g., including pure or substituted silicates, pure orsubstituted aluminosilicates, pure or substituted germanosilicates, orpure or substituted titanosilicates), further embodiments comprisingisolating these solids. These crystalline solids may be removed from thereaction mixtures by any suitable means (e.g., filtration,centrifugation, etc. or simple removal of the membrane template) anddried. Such drying may be done in air or under vacuum at temperaturesranging from 25° C. to about 200° C. Typically, such drying is done at atemperature of about 100° C.

These crystalline microporous solids may be further modified, forexample, by incorporating metals with the pore structures, either beforeor after drying, for example by replacing some of the cations in thestructures with additional metal cations using techniques known to besuitable for this purpose (e.g., ion exchange). Such cations can includethose of rare earth, Group 1, Group 2 and Group 8 metals, for exampleCa, Cd, Co, Cu, Fe, Mg, Mn, Ni, Pt, Pd, Re, Sn, Ti, V, W, Zn and theirmixtures.

Alternatively or additionally, the isolated crystalline solid may besubject to further processing, such further comprising heating theisolated crystalline microporous solid at a temperature in a range offrom about 250° C. to 300° C., from 300° C. to 350° C., from 350° C. to400° C., from 400° C. to about 450° C., or a range combining any two ormore of these ranges, to form an OSDA-depleted product. The heating maybe done in an oxidizing atmosphere, such as air or oxygen, or in thepresence of other oxidizing agents. In other embodiments, the heating isdone in an inert atmosphere, such as argon or nitrogen.

As used herein, the term “OSDA-depleted” (or composition having depletedOSDA) refers to a composition having a lesser content of OSDA after thetreatment than before. In preferred embodiments, substantially all(e.g., greater than 90, 95, 98, 99, or 99.5 wt %) or all of the OSDA isremoved by the treatment; in some embodiments, this can be confirmed bythe absence of a TGA endotherm associated with the removal of the OSDAwhen the product material is subject to TGA analysis or the absence orsubstantial absence of C or N in elemental analysis (prior to heating,expect composition to comprise C, N, O, Si, Al, H).

In those embodiments where the processing involved heating, typicalheating rates include is 0.1° C. to 10° C. per minute and or 0.5° C. to5° C. per minute. Different heating rates may be employed depending onthe temperature range. Depending on the nature of the calciningatmosphere, the materials may be heated to the indicated temperaturesfor periods of time ranging from 1 to 60 hours or more, to produce acatalytically active product.

Further processing of these materials, whether modified or not, may alsocomprise contacting the isolated crystalline microporous silicate solidwith ozone or other oxidizing agent at a temperature in a range of 100°C. to 200° C. for a time sufficient to form an OSDA-depleted silicateproduct. In certain of these embodiments, the heating is done at atemperature of about 150° C. for a time sufficient to form anOSDA-depleted product. The ozone-treatment can be carried out in a flowof ozone-containing oxygen (typically for 6 hours or more. but shortercould be feasible). Practically any oxidative environment sufficient toremove the OSDA can be used, especially those already known for thispurpose. Such environments, for example, can involve the use of organicoxidizers (alkyl or aryl peroxides or peracids) or inorganic peroxides(e.g., H₂O₂) (alkyl or aryl peroxides or peracids.

Further processing of these materials, whether modified or not, may alsocomprise, heating the isolated crystalline microporous silicate solid ata temperature in a range of from about 200° C. to about 600° C. in thepresence of an alkali, alkaline earth, transition metal, rare earthmetal, ammonium or alkylammonium salts (anions including halide,preferable chloride, nitrate, sulfate, phosphate, carboxylate, ormixtures thereof) for a time sufficient to form a dehydrated or anOSDA-depleted product. In certain of these embodiments, the heating isdone in the presence of NaCl or KCl. In certain exemplary embodiments,the heating is done at a temperature in a range of from 500 to 600° C.In exemplary embodiments, the heating is done in either an oxidizing orinert atmosphere.

Once dehydrated or calcined, the dehydrated or OSDA-depleted crystallinemicroporous material may be treated with an aqueous ammonium or metalsalt or may be treated under conditions so as to incorporate at leastone type of alkaline earth metal or alkaline earth metal oxide or salt,or transition metal or transition metal oxide. In some embodiments, thesalt is a halide salt. Where the salt is an ammonium salt, the resultingaluminosilicate may be simply protonated (in the hydrogen form). Inother embodiments, the metal salt comprises K⁺, Li⁺, Rb⁺, Cs⁺: Co²⁺,Ca²⁺, Mg²⁺, Sr²⁺; Ba²⁺; Ni²⁺; Fe²⁺. In other specific embodiments, themetal cation salt is a copper salt, for example, Schweizer's reagent(tetraamminediaquacopper dihydroxide, [Cu(NH₃)₄(H₂O)₂](OH)₂]),copper(II) nitrate, or copper(II) carbonate.

The addition of a transition metal or transition metal oxide may beaccomplished, for example by chemical vapor deposition or chemicalprecipitation. As used herein, the term “transition metal” refers to anyelement in the d-block of the periodic table, which includes groups 3 to12 on the periodic table. In actual practice, the f-block lanthanide andactinide series are also considered transition metals and are called“inner transition metals. This definition of transition metals alsoencompasses Group 4 to Group 12 elements. In certain independentembodiments, the transition metal or transition metal oxide comprises anelement of Groups 6, 7, 8, 9, 10, 11, or 12. In other independentembodiments, the transition metal or transition metal oxide comprisesscandium, yttrium, titanium, zirconium, vanadium, manganese, chromium,molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium,nickel, palladium, platinum, copper, silver, gold, or mixtures. Fe, Ru,Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof arepreferred.

Intermediate Reaction Compositions

As described herein, the as-formed and post-treated crystalline silicatecompositions themselves are within the scope of the present disclosureand are considered to be independent embodiments of the presentinvention. All of the descriptions used to describe the features of thedisclosed processes yield compositions which are separately consideredembodiments. In an abundance of caution, some of these are presentedhere, but these descriptions should not be considered to excludeembodiments provided, or which naturally follow from other descriptions.

Included in these embodiments are compositions comprising the aqueouscompositions used in the hydrothermal treatments together with therespective crystalline microporous silicate products, wherein thesilicate products contain the respective OSDAs used in their preparationoccluded in their pores.

For example, in some embodiments, the composition comprises:

-   -   (a) a source of a silicon oxide;    -   (b) an optional source of aluminum oxide;    -   (c) an optional source of germanium oxide;    -   (d) an optional source of titanium oxide;    -   (e) an optional source of one or more of boron oxide, gallium        oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,        indium oxide, vanadium oxide, zinc oxide, zirconium oxide, or        combination or mixture thereof;    -   (f) a mineralizing agent; and    -   (g) an organic structure directing agent (OSDA) comprising a        substituted benzyl-3H-imidazol-1-ium cation of Formula (I):

-   -   and    -   (h) a compositionally consistent crystalline microporous        silicate solid of LTA topology;    -   wherein    -   R¹, R², and R⁷ are independently C₁₋₆ alkyl, preferably C₁₋₃        alkyl;    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl.        The substituted benzyl-3H-imidazol-1-ium cation has an        associated anion such as otherwise described herein as        associated thereto.

As used herein, the term “compositionally consistent” refers to acrystalline silicate composition having a stoichiometry resulting fromthe crystallization of the of sources of oxides in the presence ofsubstituted benzyl-3H-imidazol-1-ium cation; i.e., the OSDAs of Formula(I). In some of these embodiments, for example, this term reflects acomposition which is the result of at least a partial progression of thehydrothermal treating process used to prepare these materials.Typically, these compositionally consistent crystalline microporous pureor optionally substituted silicate, pure or optionally substitutedaluminosilicate, pure or optionally substituted germanosilicate, or pureor optionally substituted titanosilicate solids contain, occluded intheir pores, the OSDA used to make them; i.e., the OSDA present in theassociated aqueous compositions. All such compositions are consideredwithin the scope of the present disclosure.

In separate embodiments, these compositionally consistent crystallinemicroporous silicate solids may be substantially free of the OSDAs usedin the aqueous media; in such embodiments, the optionally substitutedsilicates may be used as seed material for the crystallization, also asdescribed elsewhere herein.

These compositions may comprise any of the types, sources, and ratios ofingredients associated with a process described elsewhere herein, andmay exist at any temperature consistent with the processing conditionsdescribed above as useful for the hydrothermal processing embodiments.It should be appreciated that this disclosure captures each and every ofthese permutations as separate embodiments, as if they were separatelylisted. In some embodiments, these compositions exist in the form of asuspension. In other embodiments, these compositions exist in the formof a gel.

Crystalline Microporous Compositions

In addition to the processing and process compositions, each of thecrystalline microporous silicate products of LTA topology formedaccording to the methods described herein are also considered individualembodiments within the scope of the present invention. That is, eachcrystalline microporous product having LTA topology produced by any ofthe hydrothermal processing steps, or from any of the post-processingsteps, is considered a separate embodiment of this disclosure. Inpreferred embodiments, the crystalline microporous silicate solid ispreferably one of entirely LTA topology. Separate embodiments alsoprovide that the crystalline microporous solid may also contain otherstructural phases or phase mixtures.

These isolated microporous silicate solid of LTA topology may containany of the genera or specific substituted benzyl-3H-imidazol-1-iumcation OSDAs described herein occluded in their pores—i.e., the OSDAs ofFormula (I) within the respective framework. Such solids independentlyinclude the pure and optionally substituted silicates, pure andoptionally substituted aluminosilicates, pure and optionally substitutedgermanosilicates, and pure and optionally substituted titanosilicateshaving occluded OSDAs, the ODSAs including those of:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are defined in terms asotherwise described herein, including the structure:

In some embodiments, the isolated microporous silicate solid of LTAtopology may be devoid or substantially devoid of such organic materials(the terms “devoid” and “substantially devoid” being quantitativelyanalogous to the term “OSDA depleted”).

The presence of these OSDAs may be identified using, for example ¹³C NMRor any of the methods defined in the Examples. It is a particularfeature of the present invention that the cationic OSDAs retain theiroriginal structures, including their stereochemical conformations duringthe synthetic processes, these structures being compromised during thesubsequent calcinations or oxidative treatments.

In some embodiments, where HF or other source of fluoride is used thatthe mineralizing agent, the pores may additionally comprise fluoride (asevidenced by ¹⁹F NMR).

In certain embodiments, the aluminosilicates materials have a molarratio of Si:Al in a range of from about from 5 to 6, from 6 to 8, from 8to 10, from 10 to 14, from 14 to 18, from 18 to 22, from 22 to 26, from26 to 30, from 30 to 34, from 34 to 38, from 38 to 42, from 42 to 44,from 44 to 46, from 46 to 50, from 50 to 100, from 100 to infinity(i.e., pure silica) or a range combining any two or more of theseranges, for example, from 12 to 42. In other embodiments, thetitanosilicates have a molar ratio of Si:Ti of at least 25 (orTi:Si≦0.02, or in a range of from about 50 to 100, from 100 to 150, from150 to 250, from 250 to 500, from 500 to 1000, or a range combining anytwo or more of these ranges, for example, from 50 to 150.

The disclosed crystalline microporous silicate compositions includethose which result from the post-treatment or further processingdescribed in the processing section. These include those silicates whichare in their hydrogen forms or have cations, metals or metal oxideswithin their pore structures. Accordingly, in certain embodiments, themicroporous pure or substituted silicates, pure or substitutedaluminosilicate, pure or substituted germanosilicate, or pure orsubstituted titanosilicate having LTA topology contain Li, Na, K, Rb,Cs, Be, Mg, Ca, Sr, Be, Al, Ga, In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg,La, Ce, Pr, Nd, Pm, Sm, Eu, or R_(4-n)N⁺H_(n) cations, where R is alkyl,n=0-4 in at least some of their pores. In specific aspects of theseembodiments, these pores contain NaCl or KCl.

Additional embodiments include those crystalline microporous solidshaving LTA topologies, at least some of whose pores transition metals,transition metal oxides, or salts, for example scandium, yttrium,titanium, zirconium, vanadium, manganese, chromium, molybdenum,tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel,palladium, platinum, copper, silver, gold, or mixtures thereof, each asa metal, oxide, or salt. In one specific embodiment, the pores of thesilicate solids contain copper, as metal, oxide, or salt.

The crystalline microporous silicate solids may also characterized bytheir physical properties. In specific embodiments, the crystallinemicroporous solid exhibits one or more of the following characteristics:

-   -   (a) an XRD pattern having at least the five major peaks        substantially as provided in Table 2A or 2B;    -   (b) an XRD diffraction pattern the same as or consistent with        any one of those shown in FIG. 5, FIG. 12, or FIG. 14(A) or (B);    -   (c) unit cell substantially the same as those shown in any one        of Table 3-5;    -   (d) an ²⁹Si MAS spectrum the same as or consistent with either        of those shown in FIG. 7(A) or (B);    -   (e) an ²⁷Al MAS spectrum the same as or consistent with either        of those shown in FIG. 13(A), (B), or (C); and    -   (f) an physisorption isotherm with N₂-gas or with argon the same        as or consistent with any one of those shown in FIG. 9 (A-C).

Use of the Inventive Compositions—Catalysis

The crystalline microporous silicate solids, calcined, doped, or treatedwith the catalysts described herein may also be used as catalysts for avariety of chemical reactions. The specific pore sizes of the LTAframeworks make them particularly suited for their use in catalyzingreactions including carbonylating DME with CO at low temperatures,reducing NOx with methane (e.g., in exhaust applications), cracking,dehydrogenating, converting paraffins to aromatics, MTO, isomerizingxylenes, disproportionating toluene, alkylating aromatic hydrocarbons,oligomerizing alkenes, aminating lower alcohols, separating and sorbinglower alkanes, hydrocracking a hydrocarbon, dewaxing a hydrocarbonfeedstock, isomerizing an olefin, producing a higher molecular weighthydrocarbon from lower molecular weight hydrocarbon, reforming ahydrocarbon, converting a lower alcohol or other oxygenated hydrocarbonto produce an olefin products, epoxiding olefins with hydrogen peroxide,reducing the content of an oxide of nitrogen contained in a gas streamin the presence of oxygen, or separating nitrogen from anitrogen-containing gas mixture by contacting the respective feedstockwith the a catalyst comprising the crystalline microporous solid of anyone of the silicate (including the pure-silicates, aluminosilicates,germanosilicates, and titanosilicates) under conditions sufficient toaffect the named transformation.

The aluminosilicate solids appear to be especially suitable forconverting a lower alcohols or other oxygenated hydrocarbon into olefinproducts by contacting the corresponding feedstock with a catalystcomprising a crystalline microporous aluminosilicates described herein,under conditions sufficient to affect the named transformation.Transformations of feedstocks comprising methanol are particularlyfacile.

Crystalline microporous titanosilicates having LTA topology are alsouseful as a catalyst for epoxiding olefins with hydrogen peroxide, bycontacting the olefin with the a catalyst comprising a crystallinemicroporous titanosilicate solids, as described herein, under conditionssufficient to epoxide the olefin. In particularly useful embodiments,the olefin is an allylic alcohol.

Specific conditions for many of these transformations are known to thoseof ordinary skill in the art. Exemplary conditions for suchreactions/transformations may also be found in WO/1999/008961, and U.S.Pat. No. 4,544,538, both of which are incorporated by reference hereinin its entirety for all purposes.

Depending upon the type of reaction which is catalyzed, the microporoussolid may be predominantly in the hydrogen form, partially acidic orsubstantially free of acidity. As used herein, “predominantly in thehydrogen form” means that, after calcination (which may also includeexchange of the pre-calcined material with NH₄ ⁺ prior to calcination),at least 80% of the cation sites are occupied by hydrogen ions and/orrare earth ions.

Use of the Inventive Compositions—Other

Molecular sieves with LTA topology, such as described herein, are alsouseful in other applications including removal of H₂O, CO₂ and SO₂ fromfluid streams, such as low-grade natural gas streams, and separations ofgases, including noble gases, N₂, O₂, fluorochemicals and formaldehyde).Exemplary applications will be apparent to the skilled person upon areading of the present disclosure.

These LTA compositions may also be incorporated into polymer-compositemembranes by known methods, the polymers comprising, for example,polyimide, polyethersulfone, polyetheretherketone, and mixtures andcopolymers thereof. In other embodiments, the LTA compositions, assupported films or membranes, may be used as reaction templates,separation media, or dielectrics.

The following listing of embodiments is intended to complement, ratherthan displace or supersede, any of the previous descriptions.

Embodiment 1. A process for comprising hydrothermally treating anaqueous composition comprising:

-   -   (a) a source of a silicon oxide;    -   (b) an optional source of aluminum oxide;    -   (c) an optional source of germanium oxide;    -   (d) an optional source of titanium oxide;    -   (e) an optional source of one or more of boron oxide, gallium        oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,        indium oxide, vanadium oxide, zinc oxide, zirconium oxide, or        combination or mixture thereof;    -   (f) a mineralizing agent; and    -   (g) an organic structure directing agent (OSDA) comprising a        substituted benzyl-3H-imidazol-1-ium cation of Formula (I):

under conditions effective to crystallize a crystalline microporoussolid of LTA topology;

-   -   wherein    -   R¹, R², and R⁷ are independently C₁₋₃ alkyl;    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl.        In some Aspects of this Embodiment, the substituted        benzyl-3H-imidazol-1-ium cation has an associated bromide,        chloride, fluoride, iodide, nitrate, hydroxide, or other anion,        preferably hydroxide. Other independent Aspects of this        Embodiment provide for the absence of presence of any one or        more sources of one or more of the optional metals or        metalloids. Still other Aspects of this Embodiment include those        where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are defined        elsewhere herein.

In some Aspects of this Embodiment, the substitutedbenzyl-3H-imidazol-1-ium cation can be used in conjunction with lesseramounts of other OSDAs known to provide LTA topologies. These materialsand their relative proportions are described elsewhere herein.

Embodiment 2. The process of Embodiment 1, wherein the OSDA comprises a2,3-dialkyl-1-(4-alkyl-benzyl)-3H-imidazol-1-ium cation of Formula (IA):

Embodiment 3. The process of Embodiment 1, wherein the OSDA comprises a2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium cation of Formula(IB):

2,3-Dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium; chloride

Embodiment 4. The process of any one of Embodiments 1 to 3, wherein theaqueous composition further comprises: (b) a source of an aluminumoxide. In independent Aspects of this Embodiment, the aqueouscomposition contains only sources of silicon and aluminum oxides, and inother Aspects, the aqueous composition contains any one or more of theoptional source of the optional metal oxides.

Embodiment 5. The process of any one of Embodiments 1 to 5, wherein theaqueous composition further comprises: (c) a source of a germaniumoxide. In independent Aspects of this Embodiment, the aqueouscomposition contains only sources of silicon and germanium oxides, andin other Aspects, the aqueous composition contains any one or more ofthe optional source of the optional metal oxides.

Embodiment 6. The process of any one of Embodiments 1 to 6, wherein theaqueous composition further comprises: (d) a source of a titanium oxide.In independent Aspects of this Embodiment, the aqueous compositioncontains only sources of silicon and titanium oxides, and in otherAspects, the aqueous composition contains any one or more of theoptional source of the optional metal oxides.

Embodiment 7. The process of any one of Embodiments 1 to 3, wherein thehydrothermal treatment provides a crystalline microporous silicate solidof LTA topology. In one Aspect of this Embodiment, the crystallinemicroporous solid of LTA topology is a pure silicate, the term “pure”reflecting the absence of all but the inevitable impurities present inthe sources of silicon oxide.

Embodiment 8. The process of Embodiment 4, wherein the hydrothermaltreatment provides a crystalline microporous aluminosilicate solid ofLTA topology. In one Aspect of this Embodiment, the crystallinemicroporous solid of LTA topology is a pure aluminosilicate, the term“pure” reflecting the absence of all but the inevitable impuritiespresent in the sources of aluminum and silicon oxides

Embodiment 9. The process of Embodiment 5, wherein the hydrothermaltreatment provides a crystalline microporous germanosilicate solid ofLTA topology. In one Aspect of this Embodiment, the crystallinemicroporous solid of LTA topology is a pure germanosilicate, the term“pure” reflecting the absence of all but the inevitable impuritiespresent in the sources of germanium and silicon oxides.

Embodiment 10. The process of Embodiment 6, wherein the hydrothermaltreatment provides a crystalline microporous titanosilicate solid of LTAtopology. In one Aspect of this Embodiment, the crystalline microporoussolid of LTA topology is a pure titanosilicate, the term “pure”reflecting the absence of all but the inevitable impurities present inthe sources of silicon and titanium oxides.

Embodiment 11. The process of any one of Embodiments 1 to 10, whereinthe OSDA cation has an associated fluoride or hydroxide ion preferablysubstantially free of other halide counterions. In separate Aspects ofthis Embodiment, the associated anion is hydroxide.

Embodiment 12. The process of any one of Embodiments 1 to 11, wherein:

-   -   (a) the source of silicon oxide comprises an alkoxide, a        silicate, silica hydrogel, silicic acid, fumed silica, colloidal        silica, tetra-alkyl orthosilicate, a silica hydroxide, a silicon        alkoxide, or combination thereof;    -   (b) the source of aluminum oxide, when present, comprises an        alkoxide, hydroxide, or oxide of aluminum, a sodium aluminate,        or combination thereof;    -   (c) the source of germanium oxide, when present, comprises a        alkali metal orthogermanate, M₄GeO₄, containing discrete GeO₄ ⁴⁻        ions, GeO(OH)₃ ⁻, GeO2(OH)₂ ²⁻, [(Ge(OH)₄)₈(OH)₃]³⁻ or neutral        solutions of germanium dioxide containing Ge(OH)₄, or an        alkoxide or carboxylate derivative thereof;    -   (d) the source of titanium oxide, when present, comprises a        titanium alkoxide, oxide, or hydroxy oxide; and    -   (e) the source of boron oxide, gallium oxide, hafnium oxide,        iron oxide, tin oxide, titanium oxide, indium oxide, vanadium        oxide, zinc oxide, zirconium oxide.

Embodiment 13. The process of any one of Embodiments 1 to 12, whereinthe mineralizing agent is or comprises an aqueous hydroxide.

Embodiment 14. The process of any one of Embodiments 1 to 12, whereinthe mineralizing agent is or comprises hydrofluoric acid (HF). Indifferent aspects of this Embodiment, the HF is added as such orgenerated in situ using fluoride sources in the presence of strongacids.

Embodiment 15. The process of any one of Embodiments 1 to 14, wherein:

-   -   (a) the molar ratio of the OSDA:Si is in a range of from 0.1 to        1, preferably in a range of from 0.4 to 0.6;    -   (b) the molar ratio of Al:Si is in a range of from 0 to 0.1 or        0.005 to 0.1 (or Al is absent or Si/Al=10 to 200)    -   (c) the molar ratio of Ge:Si is in a range of from 0 to 1 or        0.05 to 1 (or Ge is absent or Si/Ge=1 to infinity or 1 to 20);        or    -   (d) the molar ratio of Ti:Si is in a range of from 0 to 0.1 or        0.01 to 0.1 (or Si/Ge=1 to infinity or 1 to 20).

Embodiment 16. The process of any one of Embodiments 1 to 15, wherein:

-   -   (e) the molar ratio of water:Si is in a range of from about 2 to        about 50, preferably in a range of from about 4 to about 10.

Embodiment 17. The process of any one of Embodiments 1 to 16, wherein:

-   -   (f) the molar ratio of OSDA:Si is in a range of from about 0.1        to about 0.75, preferably in a range of from about 0.4 to about        0.6.

Embodiment 18. The process of any one of Embodiments 1 to 17, whereinthe mineralizing agent is HF and:

-   -   (g) the molar ratio of fluoride:Si is in a range of from about        0.1 to about 0.75, preferably in a range of from about 0.4 to        about 0.6.

Embodiment 19. The process of any one of Embodiments 1 to 18, whereinthe conditions effective to crystallize a crystalline microporous LTAtopology include treatment of the respective hydrothermally treatedaqueous composition at a temperature in a range of from 100° C. to 200°C. In certain Aspects of this Embodiment, the temperature is in a rangeof from, 120° C. to 160° C., for a time effective for crystallizing thecrystalline microporous solid of LTA topology. In certain Aspects ofthis Embodiment, the times and temperatures include ranges describedelsewhere herein.

Embodiment 20. The process of any one of Embodiments 1 to 19, whereinthe conditions effective to crystallize a crystalline microporous LTAtopology include treatment of the respective hydrothermally treatedaqueous composition at a temperature in a range of from 100° C. to 200°C. for a time in a range of from 3 to 40 days, preferably from 7 to 40days.

Embodiment 21. The process of any one of Embodiments 1 to 20, furthercomprising isolating the crystalline microporous solid of LTA topology.

Embodiment 22. The process of Embodiment 21, wherein the isolated thecrystalline microporous solid of LTA topology is a pure silicate, analuminosilicate, a germanosilicate, or a titanosilicate. In otherAspects of this embodiment, the isolated microcrystalline is describedas a silicate or heteratom-substituted silicate, as defined herein.

Embodiment 23. The process of Embodiment 21 or 22, further comprising:

-   -   (a) heating the isolated crystalline microporous solid at a        temperature in a range of from about 250° C. to about 450° C.;    -   (b) contacting the isolated crystalline microporous solid with        ozone or other oxidizing agent at a temperature in a range of        100° C. to 200° C.;    -   or    -   (c) heating the isolated crystalline microporous solid at a        temperature in a range of from about 200° C. to about 600° C. in        the presence of an alkali, alkaline earth, transition metal,        rare earth metal, ammonium or alkylammonium salt;    -   for a time sufficient to form a dehydrated or an OSDA-depleted        product.

Embodiment 24. The process of Embodiment 23, further comprising:

-   -   (a) treating the dehydrated or OSDA-depleted product with an        aqueous alkali, alkaline earth, transition metal, rare earth        metal, ammonium or alkylammonium salt, as described elsewhere        herein; and/or    -   (b) treating the dehydrated or OSDA-depleted product with at        least one type of transition metal or transition metal oxide, as        described elsewhere herein.

Embodiment 25. A composition prepared by a process of Embodiment 21 or22. In one Aspect of this Embodiment, the composition comprises aplurality of loose crystalline microporous solid. In another Aspect ofthis Embodiment, the composition comprises a film or membrane of thenamed composition.

Embodiment 26. A composition prepared by the process of Embodiment 23.

Embodiment 27. A composition prepared by the process of Embodiment 24.

Embodiment 28. A composition comprising:

-   -   (a) a source of a silicon oxide;    -   (b) an optional source of aluminum oxide;    -   (c) an optional source of germanium oxide;    -   (d) an optional source of titanium oxide;    -   (e) an optional source of one or more of boron oxide, gallium        oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,        indium oxide, vanadium oxide, zinc oxide, zirconium oxide, or        combination or mixture thereof;    -   (f) a mineralizing agent; and    -   (g) an organic structure directing agent (OSDA) comprising a        substituted benzyl-3H-imidazol-1-ium cation of Formula (I):

-   -   and    -   (h) a compositionally consistent crystalline microporous        silicate solid of LTA topology;    -   wherein    -   R¹, R², and R⁷ are independently C₁₋₆ alkyl, preferably C₁₋₃        alkyl;    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl;        and        the substituted benzyl-3H-imidazol-1-ium cation has an        associated bromide, chloride, fluoride, iodide, nitrate, or        hydroxide anion. Independent Aspects of this Embodiment include        those compositions in which the sources and ratios of the source        or optional sources of metal oxides are as describe elsewhere        herein.

Embodiment 29. The composition of Embodiment 28, wherein the OSDAcomprises a 2,3-dialkyl-1-(4-alkyl-benzyl)-3H-imidazol-1-ium cation ofFormula (IA):

Embodiment 30. The composition of Embodiment 28, wherein the OSDAcomprises a 2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium cation ofFormula (IB):

Embodiment 31. The composition of any one of Embodiments 28 to 30,wherein the aqueous composition further comprises:

-   -   (b) a source of an aluminum oxide; and    -   (h) a compositionally consistent crystalline microporous        aluminosilicate solid of LTA topology.

Embodiment 32. The composition of any one of Embodiments 28 to 31,wherein the aqueous composition further comprises:

-   -   (c) a source of a germanium oxide; and    -   (h) a compositionally consistent crystalline microporous        germanosilicate solid of LTA topology.

Embodiment 33. The composition of any one of Embodiments 28 to 32,wherein the aqueous composition further comprises:

-   -   (d) a source of a titanium oxide; and    -   (h) a compositionally consistent crystalline microporous        titanosilicate solid of LTA topology.

Embodiment 34. The composition of any one of Embodiments 28 to 33,wherein the mineralizing agent is or comprises an aqueous hydroxide, forexample an aqueous alkali metal or alkaline earth metal hydroxide.

Embodiment 35. The composition of any one of Embodiments 28 to 33,wherein the mineralizing agent is or comprises hydrofluoric acid (HF).

Embodiment 36. The composition of any one of claims 17-22, wherein:

-   -   (a) the molar ratio of OSDA:Si is in a range of from 0.1 to 1,        preferably in a range of from 0.6 to 0.6;    -   (b) the molar ratio of Al:Si is in a range of from 0 to 0.1 or        0.005 to 0.1 (or Al is absent or Si/Al=10 to 200)    -   (c) the molar ratio of Ge:Si is in a range of from 0 to 1 or        0.05 to 1 (or Ge is absent or Si/Ge=1 to infinity or 1 to 20);        or    -   (d) the molar ratio of Ti:Si is in a range of from 0 to 0.1 or        0.01 to 0.1 (or Si/Ge=1 to infinity or 1 to 20).

Embodiment 37. The composition of any one of Embodiments 28 to 36,wherein:

-   -   (e) the molar ratio of water:Si is in a range of from about 2 to        about 50, preferably in a range of from about 4 to about 10.

Embodiment 38. The composition of any one of Embodiments 28 to 37,wherein:

-   -   (f) the molar ratio of OSDA:Si is in a range of from about 0.1        to about 0.75, preferably in a range of from about 0.4 to about        0.6.

Embodiment 39. The composition of any one of Embodiments 28 to 38,wherein the mineralizing agent is HF and:

-   -   (g) the molar ratio of fluoride:Si is in a range of from about        0.1 to about 0.75, preferably in a range of from about 0.4 to        about 0.6.

Embodiment 40. The composition of any one of Embodiments 28 to 39, thatis present at a temperature in a range of from 100° C. to 200° C.,preferably from 125° C. to 160° C.

Embodiment 41. The composition of any one of Embodiments 28 to 40 thatis a suspension or a gel.

Embodiment 42. A crystalline microporous silicate solid of LTA topologycontaining within its pores an OSDA comprising substitutedbenzyl-3H-imidazol-1-ium cation of Formula (I):

-   -   wherein    -   R¹, R², and R⁷ are independently C₁₋₆ alkyl, preferably C₁₋₃        alkyl; and    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl.

Embodiment 43. A crystalline microporous aluminosilicate solid of LTAtopology containing within its pores an OSDA comprising a substitutedbenzyl-3H-imidazol-1-ium cation of Formula (I):

-   -   wherein    -   R¹, R², and R⁷ are independently C₁₋₆ alkyl, preferably C₁₋₃        alkyl; and    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl.

Embodiment 44. A crystalline microporous germanosilicate solid of LTAtopology containing within its pores an OSDA comprising a substitutedbenzyl-3H-imidazol-1-ium cation of Formula (I):

-   -   wherein    -   R¹, R², and R⁷ are independently C₁₋₆ alkyl, preferably C₁₋₃        alkyl; and    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl.        Other Aspects of this Embodiment, with respect to the        definitions of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are        described herein.

Embodiment 45. A crystalline microporous titanosilicate solid of LTAtopology containing within its pores an OSDA comprising a substitutedbenzyl-3H-imidazol-1-ium cation of Formula (I):

-   -   wherein    -   R¹, R², and R⁷ are independently C₁₋₆ alkyl, preferably C₁₋₃        alkyl; and    -   R³, R⁴, R⁵, R⁶, R⁸, and R⁹ are independently H or C₁₋₃ alkyl.

Embodiment 46. The crystalline microporous solid of LTA topology of anyone of Embodiments 42 to 45, wherein the OSDA comprises a2,3-dialkyl-1-(4-alkyl-benzyl)-3H-imidazol-1-ium cation of Formula (IA):

Embodiment 47. The crystalline microporous solid of LTA topology of anyone of Embodiments 42 to 46, wherein the OSDA comprises a2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium cation of Formula(IB):

Embodiment 48. The crystalline microporous solid of LTA of Embodiments42 to 47, further containing within its pores fluoride ion.

Embodiment 49. A crystalline microporous pure-silicate, aluminosilicate,germanosilicate, or titanosilicate solid of LTA topology, prepared byany of the processes described herein, that is substantially free of anOrganic Structure Directing Agent (OSDA). In certain Aspects of thisEmbodiment, the aluminosilicates product has a molar ratio of Si:Al in arange of from about 5 to 6, from 6 to 8, from 8 to 10, from 10 to 14,from 14 to 18, from 18 to 22, from 22 to 26, from 26 to 30, from 30 to34, from 34 to 38, from 38 to 42, from 42 to 44, from 44 to 46, from 46to 50, or a range combining any two or more of these ranges, forexample, from 12 to 42

Embodiment 50. The crystalline microporous pure-silicate,aluminosilicate, germanosilicate, or titanosilicate solid of LTAtopology of Embodiment 49, comprising pores, at least some of whichcontain Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Be, Al, Ga, In, Zn, Ag, Cd,Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, or R_(4-n)N⁺H_(n)cations, where R is alkyl, n=0-4. In specific Aspects of thisEmbodiment, the pores contain NaCl or KCl.

Embodiment 51. The crystalline microporous solid of Embodiment 49 or 50,comprising pores, at least some of which contain scandium, yttrium,titanium, zirconium, vanadium, manganese, chromium, molybdenum,tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel,palladium, platinum, copper, silver, gold, or a mixture thereof, each asa metal, oxide, or salt. In one Aspect of this Embodiment, the porescontain copper, as metal, oxide, or salt.

Embodiment 52. The crystalline microporous silicate, aluminosilicate,germanosilicate, or titanosilicate solid of LTA topology of any one ofEmbodiments 49 to 51, the solid exhibiting one or more one of thefollowing characteristics:

-   -   (a) an XRD pattern having at least the five major peaks        substantially as provided in Table 2A or 2B;    -   (b) an XRD diffraction pattern the same as or consistent with        any one of those shown in FIG. 5, FIG. 12, or FIG. 14(A or B);    -   (c) unit cell substantially the same as those shown in any one        of Tables 3-5;    -   (d) an ²⁹Si MAS spectrum the same as or consistent with either        of those shown in FIG. 7(A) or (B);    -   (e) an ²⁷Al MAS spectrum the same as or consistent with either        of those shown in FIG. 13(A) or (B); and    -   (f) an physisorption isotherm with N₂-gas or with argon the same        as or consistent with any one of those shown in FIG. 7 (A-C).

Embodiment 53. A process comprising carbonylating DME with CO at lowtemperatures, reducing NOx with methane, cracking, dehydrogenating,converting paraffins to aromatics, MTO, isomerizing xylenes,disproportionating toluene, alkylating aromatic hydrocarbons,oligomerizing alkenes, aminating lower alcohols, separating and sorbinglower alkanes, hydrocracking a hydrocarbon, dewaxing a hydrocarbonfeedstock, isomerizing an olefin, producing a higher molecular weighthydrocarbon from lower molecular weight hydrocarbon, reforming ahydrocarbon, converting a lower alcohol or other oxygenated hydrocarbonto produce an olefin products, epoxiding olefins with hydrogen peroxide,reducing the content of an oxide of nitrogen contained in a gas streamin the presence of oxygen, or separating nitrogen from anitrogen-containing gas mixture by contacting the respective feedstockwith the a catalyst comprising the crystalline microporous solid of anyone of Embodiments 49 to 52 under conditions sufficient to affect thenamed transformation.

Embodiment 54. The process of Embodiment 53, comprising converting alower alcohol or other oxygenated hydrocarbon to produce an olefinproducts by contacting the respective feedstock with the a catalystcomprising any one of the crystalline microporous aluminosilicate solidsof Embodiments 49 to 52 under conditions sufficient to affect the namedtransformation.

Embodiment 55. The process of Embodiment 53, wherein the lower alcoholor other oxygenated hydrocarbon is methanol.

Embodiment 56. The process of Embodiment 53, comprising epoxiding anolefin with hydrogen peroxide, by contacting the olefin with the acatalyst comprising any one of the crystalline microporoustitanosilicate solids of Embodiments 49 to 52 under conditionssufficient to epoxide the olefin.

Embodiment 57. The process of Embodiment 56, wherein the olefin is anallylic alcohol.

Embodiment 58. A process comprising removing of H₂O, CO₂ and SO₂ fromfluid streams, such as low-grade natural gas streams, and separatinggases, including noble gases, N₂, O₂, fluorochemicals and formaldehyde,from gas streams.

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees Celsius, pressure is ator near atmospheric.

Example 1 Materials and Methods

Unless otherwise noted, all reagents were purchased from commercialsources and were used as received. Unless otherwise noted all, reactionswere conducted in flame-dried glassware under an atmosphere of argon.Hydroxide ion exchanges were performed using Supelco Dowex Monosphere550A UPW hydroxide exchange resin with an exchange capacity of 1.1meq/mL. Titrations were performed using a Mettler-Toledo DL22autotitrator using 0.01 M HCl as the titrant. All liquid NMR spectrawere recorded with a 400 MHz Varian Spectrometer. Liquid NMR spectrawere recorded on Varian Mercury spectrometers.

All powder x-ray diffraction characterization were conducted on a RigakuMiniFlex II diffractometer with Cu Kα radiation.

Solid-state NMR (¹³C, ¹⁹F, ²⁷Al and ²⁹Si) spectra were obtained using aBruker DSX-500 spectrometer (11.7 T) and a Bruker 4 mm MAS probe. Thespectral operating frequencies were 500.2 MHz, 125.721 MHz, 470.7 MHz,130.287 MHz and 99.325 MHz for ¹H, ¹³C, ¹⁹F, ²⁷Al and ²⁹Si nuclei,respectively. Spectra were referenced to external standards as follows:tetramethylsilane (TMS) for ¹H and ²⁹Si, adamantane for ¹³C as asecondary external standard relative to tetramethylsilane, CFCl₃ for ¹⁹Fand 1.0 M Al(NO₃)₃ aqueous solution for ²⁷Al. Samples were spun at 14kHz for 1H and ²⁷Al MAS NMR and 8 kHz for ¹³C and ²⁹Si MAS and CPMAS NMRexperiments. ¹⁹F MAS NMR spectra were collected at both 13 and 15 kHz toassign spinning side bands. For detection of the ²⁷Al signal, a short0.5 μs-/18 pulse was used before FID was recorded in order to makequantitative comparison among resonances.

Thermogravimetric analysis (TGA) was performed on a Perkin Elmer STA6000 with a ramp of 10° C.min⁻¹ to 900° C. under air atmosphere. Samples(0.01-0.06 g) were placed in aluminum crucible and heated at 1 K/min ina flowing stream (0.667 cm³/s) comprised of 50% air (Air Liquide,breathing grade) and 50% argon (Air Liquide, UHP).

SEM analyses were performed on a ZEISS 1550 VP FESEM, equipped with anOxford X-Max SDD X-ray Energy Dispersive Spectrometer (EDS) system fordetermining the Si/Al ratios of the samples.

Example 2 Synthesis of 1,2-dimethyl-3-(4-methylbenzyl)-1H-imidazol-3-iumhydroxide

The 1,2-dimethyl-3-(4-methylbenzyl)-1H-imidazol-3-ium hydroxide wassynthesized according to the scheme shown in FIG. 3. A 500 mL flask wascharged with 1,2-dimethyl imidazole (11.60 grams, 121.0 mmols),4-methylbenzyl chloride (15.46 grams, 110.0 mmols) and toluene(125 mL).The flask was fitted with a reflux condenser and heated to reflux for 15hours. The reaction was cooled to 25° C. and resulting solids werefiltered and washed with ethyl acetate (3×50 mL) to give the OSDA (24.10grams, 92% yield) as a white solid. ¹H NMR (500 MHz, CD₃OD): δ 7.54-7.53(m, 2H), 7.28 (d, J=5.0, 2H), 7.28 (d, J=5.0, 2H), 5.34 (s, 2H), 3.87(s, 3H), 2.67 (s, 3H), 2.39 (s, 3H). ¹³C NMR (126 MHz, CD3OD) δ 144.8,138.8, 130.7, 129.5, 127.6, 122.4, 121.1, 51.2, 34.1, 19.7, 8.4.

The OSDA was then converted to hydroxide form using hydroxide exchangeresin (Dowex Marathon A, hydroxide form) in water, and the product wastitrated using a Mettler-Toledo DL22 autotitrator using 0.01 M HCl asthe titrant.

Example 3 Syntheses of Molecular Sieves Example 3.1 General SyntheticMethods (FIG. 2)

A general synthesis procedure for fluoride syntheses was as follows.Tetraethylorthosilicate (TEOS), tetramethylammonium hydroxide (ifnecessary) and aluminopropoxide (if necessary) were added to the organicin its hydroxide form. The container was closed and stirred for at least12 hours to allow for complete hydrolysis. The lid was then removed andthe ethanol and appropriate amount of water were allowed to evaporateunder a stream of air. It was assumed that all the ethanol evaporatedalong with the water. Once the appropriate mass was reached the materialwas transferred to a Teflon Parr Reactor and aqueous HF was added andthe mixture was hand-stirred until a homogenous gel was obtained. Ifdesired, seeds were added at this point. The autoclave was sealed andplaced in a rotating oven at temperatures ranging from 140 to 175° C.Aliquots of the material were taken periodically by first quenching thereactor in water and then removing enough material for powder x-raydiffraction (PXRD).

Example 3.1 Synthesis of Germanosilicates

All reactions were performed in 23 mL Teflon-lined stainless steelautoclaves (Parr instruments). Reactions were performed statically ortumbled at 43 rpm using spits built into convection ovens. Syntheseswere performed at 125, 140, 150, 160, or 175° C. Silicon source wastetraethyl orthosilicate (TEOS, 99.9% Si(OCH₂CH₃)₄, Strem). Germaniumsource was germanium oxide (99.99% GeO₂, Strem).

Gels for the germanosilicate reactions were prepared by adding germaniumoxide to a solution of OSDA in water directly in the 23 mL Teflon liner.This mixture was stirred at 25° C. for 5 minutes, or until the germaniumoxide dissolved into the solution. TEOS was then added, the reactionvessel was capped, and stirred for an additional 12 hours to hydrolyzethe TEOS. The reaction vessel was then uncapped and a stream of air wasblown over the gel while it was mechanically stirred until theappropriate excess of water and hydrolyzed ethanol had been evaporated.In certain cases, the gel was put under vacuum to remove small amountsof residual water, when evaporation failed to remove the appropriateamount of water. Hydrofluoric acid was then added in a drop wise fashionto the gel, the gel was quickly stirred with a Teflon spatula, and theTeflon liner was sealed into the stainless steel autoclave and put intothe oven. The reactors were opened every 6-7 days to assess reactionprogress. After homogenizing, a small sample was successively washedwith D.I. H₂O (2×10 mL) and acetone: methanol (1:1, 3×10 mL). The PXRDpattern of the resulting product was inspected. All reactions weremonitored for at least 1 month or until a crystalline product wasobserved.

Example 3.2 Synthesis of Pure-Silica LTA

Pure-silica materials were prepared in the same manner asgermanosilicate materials except that the addition of GeO₂ was omitted.

Example 3.2 Synthesis of Aluminosilicate LTA

Aluminosilicate materials were prepared in the same manner asgermanosilicate materials except that the addition of GeO₂ was omittedand aluminum isopropoxide was used as the aluminum source (99.9%Al(O-iPr)₃, Sigma Aldrich).

Example 3.2 Synthesis of Synthesis of Titanosilicate LTA

Titanosilicate materials were prepared in the same manner asgermanosilicate materials except that the addition of GeO₂ was omittedand titanium(IV) butoxide was used as the titanium source.

The synthetic parameters used to make these LTA materials and theresulting materials are described in Table 1.

TABLE 1 Synthesis results. In each case, the molar ratio of H₂O/Si was 5and the molar ratio of HF/Si was 0.5. TMA is tetramethylammoniumhydroxide. The OSDA was 2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium hydroxide. Si/Al Gel Ratios ConditionsProduct Ref. # Si/Al Si/Ge Si/Ti TMA/Si OSDA/Si Seeds Temp., Days Resultratio 1 — 2 — — 0.5 — 160° C. 14 BEC 2 — 4 — — 0.5 — 160° C. 14 BEC 3 —8 — — 0.5 — 160° C. 14 LTA 4 — 16 — — 0.5 — 160° C. 14 LTA/ BEA 5 — 16 —— 0.5 — 140° C. 14 LTA 6 ∞ — — 0.05 0.45 — 125° C. 7 LTA — 7 ∞ — — 0.050.45 Silica 125° C. 7 LTA — LTA 8 ∞ — — — 0.5 Silica 125° C. 14 LTA —LTA 9 ∞ — — — 0.5 — 160° C. 14 LTA — 10 ∞ — — — 0.5 — 160° C. 40 None —11 ∞ — — — 0.5 — 140° C. 40 None — 12 ∞ — — 0.25 0.25 — 125° C. 7 AST —13 20 — — 0.05 0.45 Silica 125° C. 9 LTA 12 LTA 14 50 — — 0.05 0.45Silica 125° C. 7 LTA 33 LTA 15 75 — — 0.05 0.45 Silica 125° C. 7 LTA 38LTA 16 100  — — 0.05 0.45 Silica 125° C. 7 LTA 42 LTA 17 — — 100 Silica125° C. LTA LTA

For these fluoride-mediated reactions, the total organic content washeld constant for all syntheses. LTA was first identified as a productin the germanium-containing syntheses, perhaps not surprising, asgermanium is known to favor the formation of double four rings [D4Rs]and the entire LTA structure can be formed from D4Rs. Additionally, itwas found that the formation of LTA was favored at lower temperatures,as BEC formed instead at higher temperatures even in germanosilicatesystems.

The synthesis of pure-silica LTA was favored by either seeding thesyntheses or by adding a small amount of tetramethyl ammonium hydroxide(TMAOH) (see Table 1). The addition of TMAOH helped form pure-silicaLTA, but it was added in small amounts to avoid the formation of AST.Additionally, the use of seeds at lower synthesis temperatures helped toavoid the formation of competing phases. The water content was heldconstant for all syntheses, as the ratio used is easy to obtain in thesetypes of reactions.

Using this new OSDA, the synthesis of ITQ-29 is much simpler thanpreviously reported, as the new methodology has a much higher watercontent and a lower amount of TMA, avoiding the competing formation ofAST.

Example 4 Characterizations of Products Example 4.1 Pure-SilicateMaterials Example 4.1.1 Scanning Electron Microscopy (SEM) andEnergy-Dispersive X-Ray Spectroscopy (EDS)

The morphology of a pure silicate material was studied using SEM and arepresentative micrograph is shown in FIG. 4.

Example 4.1.2 Powder X-ray Diffraction (PXRD) Analysis

Powder X-ray diffraction (PXRD) patterns of the as-made and calcinedpure-silica LTA are shown in FIG. 5. It was confirmed by ¹³C CP-MAS NMRthat both the OSDA and TMA were occluded intact in the as-made material(FIG. 6). Tabulated PXRD data are provided in Tables 2A and 2B.

TABLE 2A Tabulated PXRD data for a compositions of LTA topology.Relative intensities subject to variation. Values presented here forcalcined materials. 2-theta Relative Intensity  7.3 ± 0.3 1000 10.4 ±0.3 420 12.8 ± 0.3 330 16.6 ± 0.3 70 21.1 ± 0.3 80 22.4 ± 0.3 164 24.7 ±0.3 80 28.0 ± 0.3 35 31.0 ± 0.3 40 31.9 ± 0.3 20

TABLE 2B Tabulated PXRD data for a compositions of LTA topology.Relative intensities subject to variation. Values presented here foras-made materials. 2-theta Relative Intensity  7.6 ± 0.3 1000 10.6 ± 0.3430 13.0 ± 0.3 940 15.1 ± 0.3 190 21.4 ± 0.3 210 22.7 ± 0.3 840 25.1 ±0.3 280 27.3 ± 0.3 130 28.3 ± 0.3 190 31.3 ± 0.3 140

Example 4.1.3 Nuclear Magnetic Resonance

The ²⁹Si Bloch Decay NMR of the as-made (FIG. 7(A)) and calcinedpure-silicate material (FIG. 7(B)) revealed a single resonance at −113.3ppm, consistent with the single T-site in the LTA structure, and veryfew defects.

The ¹⁹F NMR of the as-made material ((FIG. 8) showed a single resonanceat −39 ppm, consistent with the fluoride anion being occluded in thedouble four rings (D4Rs) of the LTA.

Example 4.1.4 Isotherm Data

The calcined material was characterized by argon and nitrogen adsorptionisotherms obtained at −196° C. and −186° C. respectively, with aQuantachrome Autosorb iQ instrument. Prior to analysis, the samples wereoutgassed under vacuum at 200° C. The t-plot method was used tocalculate the micropore volumes on the adsorption branch. The resultsshown in FIGS. 9(A-C) are consistent with the expected values. The argonadsorption isotherm shows a sharp, low-pressure transition, consistentwith well-defined 8MRs.

Example 4.1.5 Computational Analysis for Pure-Silicate LTA

The role of the OSDA was also studied computationally. TGA analysis FIG.10 shows that two molecules are occluded per unit cell of LTA. Thisknowledge and the fact that the OSDA is too large to fit in the smallsodalite cage means that two molecules of OSDA are occluded in eachα-cage. Molecular dynamics calculations showed that the stabilizationenergy (i.e., the difference in energy of the zeolite with occludedOSDAs and the isolated zeolite and OSDAs) was an advantageous −16.9kJ/(mol Si). The molecular modelling agreed well with the occupancydetermined by TGA as the stabilization energy was only −7.36 kJ/(mol Si)if a single OSDA is occluded per cage. For methylated julolidine amaximum stabilization energy of −14.27 kJ/(mol Si) and an averagestabilization energy of −13.03 kJ/(mol Si) were found. The molecularmodelling showed that the conformation of the methyl groups was mostlikely different than has been previously reported since the most stableconformation in the α-cage was with the methyl groups pointing away fromthe dimerization complex, not towards the complex as was assumed basedupon the single crystal structure of the pure organic. The molecularmodelling also agreed with previous studies that found AST as theproduct if the methylated julolidine did not dimerize properly as thestabilization energy for a single OSDA per cage is only −6.35 kJ/(molSi), reinforcing the idea that the dimerization of the OSDA to form asupramolecular complex is key to the formation of LTA. The molecularmodelling showed how this relatively simple OSDA was able to fill such alarge cavity, in a similar manner to the supramolecular assembly formedfrom methylated julolidine.

Example 4.5 Single Crystal X-Ray Crystallography

The as-made materials (with and without TMA in the synthesis) as well asthe calcined material were studied using single crystal X-raydiffraction. The unit cell parameters are shown for each of the samplesin Tables 3, 4, and 5, respectively. In the as-made material containingTMA, the structure analysis confirmed that TMA was present in thesodalite cages (though not all are occupied) and that the carbon atomswere completely disordered. The cages were symmetrical, so there was noreason that long range order with respect to the LTA structure should beexpected. It was also found that the fluoride location could be resolvedto the D4Rs in both as-made materials; the preferential location offluoride in D4Rs has been often reported and is normally given as onereason that fluoride-mediated syntheses lead to many structurescontaining D4Rs.

Even lowering the symmetry of the structure did not help to resolve thelocation of the disordered OSDAs. As the large α-cage of LTA is verysymmetrical, it was unlikely that the organic material would adopt anysymmetrical, long range conformation so this result was also expected,but meant that the single crystal analysis could not be used to confirmthe results of the molecular modelling study.

TABLE 3 Unit cell data at −173° C. for Sample No. P15133 (as-made, noTMA used in pure-silica LTA synthesis). Crystal system Cubic Space groupPm-3m a 11.813(3)Å α 90° b 11.813(3)Å β 90° c 11.813(3)Å γ 90° V1648.5(13)Å3 Z 24 Dc 1.491 g · cm⁻¹

TABLE 4 Unit cell data at −173° C. for Sample No. P15134 (as-made, TMAused in pure-silica LTA synthesis) Crystal system Cubic Space groupPm-3m a 11.824(5)Å α 90° b 11.824(5)Å β 90° c 11.824(5)Å γ 90° V1653(2)Å3 Z 24 Dc 1.57 g · cm⁻¹

TABLE 5 Unit cell data at −173° C. for Sample No. P15133 (Calcinedpure-silica LTA) Crystal system Cubic Space group Pm-3m a 11.857(4)Å α90° b 11.857(4)Å β 90° c 11.857(4)Å γ 90° V 1667.0(17)Å3 Z 24 Dc 1.437 g· cm⁻¹

Example 4.2

Crystalline Aluminosilicate Material where Si:Al=30.8.

Example 4.2.1

Scanning Electron Microscopy (SEM) and: As described above, themorphology of one of the aluminosilicate materials was studied usingscanning electron microscopy (SEM) and the Si/Al ratio of thecrystalline products was determined using energy-dispersive X-rayspectroscopy (EDS). SEM images can be found in FIG. 11. The averagemolar ratio of Si:Al for the material with gel having a molar ratio ofSi:Al of 50 was found to be 30.8.

Example 4.2.2

A representative powder X-ray diffraction pattern (PXRD) of one of thealuminosilicate LTA materials obtained is shown in FIG. 12 along withthe calcined material. All peaks match the reported spectra for LTA.

Example 4.2.3

The aluminosilicate material was further characterized by solid stateNMR. Solid state ²⁷Al NMR of one of the aluminosilicate LTA samplesshowed that all of the aluminum was in a tetrahedral coordinationenvironment (FIG. 13). Samples of aluminosilicate LTA were synthesizedin fluoride media over a wide product compositional range (productSi/Al=12-42, see Table 1). The sample used as the source of the NMR inFIG. 13(C) was a calcined sample containing the largest amount ofaluminum (Si/Al=12). Even in this case, the ²⁷Al MAS NMR spectrum showedthat nearly all of the aluminum was tetrahedral and thereforeincorporated in the framework.

Example 4.3

Germanosilicate and Titanosilicate Materials

Representative powder X-ray diffraction pattern (PXRD) of two of thegermanosilicate LTA materials obtained from different gel compositionsare shown in FIG. 14. All peaks match the reported spectra for LTA.

Lewis acidic LTA was prepared by the addition of titanium as aheteroatom. The incorporation of titanium was studied through DiffuseReflectance (DR)-UV spectroscopy (FIG. 15), showing tetrahedral(framework) titanium. This material may have possible applications inlow temperature oxidations of small molecules where the 8 MR ring andlarge, spherical cage size and may show advantages over larger porematerials such as TS-1 and Ti-BEA. Ti-LTA was shown to be catalyticallyactive for epoxidation reactions by using it as a catalyst for theepoxidation of allyl alcohol with H₂O₂.

Example 5 MTO Reactivity Example 3.1 Methods

Prior to reaction testing, samples were calcined in breathing-grade airby initially holding them at 150° C. for 3 h (at a heating rate of 1°C./min) before heating the samples further to 580° C. for 6 h (again ata 1° C./min heating rate) to convert them to their proton forms.Calcined samples were then pelletized, crushed, and sieved. Particlesbetween 0.6 and 0.18 mm were supported between glass wool beds in anAutoclave Engineers BTRS, Jr. SS-316 tubular, continuous flow reactor.All catalysts were dried at 150° C. in situ in a 30 cm³/min flow of 5%Ar/95% He for 4 h prior to the reaction. The reactions were conducted at400° C. in a 10% methanol/inert flow. Methanol was introduced via aliquid syringe pump at 5.4 μL/min into a gas stream of the inert blendat 30 cm3/min. The reactant flow had a weight hourly space velocity of1.3 h⁻¹. In a typical run, 200 mg of dry catalyst was loaded. Effluentgases were evaluated using an on-stream GC/MS (Agilent GC 6890/MSD5793N)with a Plot-Q capillary column installed. Conversions and selectivitieswere computed on a carbon mole basis.

Example 5.2

Preliminary time-on-stream (TOS) reaction data are shown for thecalcined aluminosilicate LTA in FIG. 16. The calcined LTA (Si/Al=30.8),while initially active in producing C₂-C₄ olefins, also produces a largeamount of C1-C4 alkanes. This sample deactivated rapidly (approximately70 min TOS), accompanied by drops in olefin selectivities and asimultaneous rise in dimethyl ether (DME) production.

Example 5.3

A more expanded investigation into the MTO reaction involved the use offour different samples of LTA with product Si/Al=12, 33, 38, 42. Theresults are compared to SSZ-13, SAPO-34 and aluminosilicate RTH (seebelow). The time dependent reaction profiles for each the materials aredifferent and data are listed in Table 6 for comparison at around 50minutes. Additional data are provided for SSZ-13, SAPO-34 and RTH thathad longer lifetimes than the LTAs. The respective profiles are shown inFIGS. 17(A-D) and FIGS. 18(A-D).

Some interesting comparisons can be made between the various frameworks.SSZ-13 and SAPO-34 show the highest maximum olefin selectivity, and havea high selectivity to ethylene and propylene. RTH gives a lowerselectively to ethylene, but higher selectivity to butenes as well as C5and C6 products. Aluminosilicate LTA shows a relatively low selectivelyto ethylene and propylene, but produces the highest selectively tobutenes as well as C5 and C6 products. Both the reaction selectivitiesand faster deactivation times appear to be related to the larger cage.

TABLE 6 MTO reaction results at maximum C2 to C4 olefin selectivity.Full reaction profiles for each material can be found in FIGs. 17(A-D)and FIGs. 18(A-D). TOS is Time on Stream. SSZ-13, SAPO-34, and RTHsamples were prepared according to the methods of J. E. Schmidt, M. A.Deimund, M. E. Davis, Chem. Mater. 2014, 26, 7099-7105 Selectivities TOSMethanol C₂-C₄ C₁-C₄ Material Si/Al (min) conversion Olefins EthylenePropylene Butenes^(a) Unsaturates^(b) C₅ + C₆ ^(c) LTA 12 51 7 0.60 0.180.16 0.25 0.18 0.22 LTA 33 53 0.93 0.72 0.24 0.24 0.25 0.15 0.13 LTA 3845 0.94 0.72 0.24 0.25 0.23 0.15 0.13 LTA 42 43 0.97 0.73 0.24 0.24 0.240.15 0.13 SSZ-13 19 48 1.00 0.69 0.19 0.19 0.15 0.22 0.09 19 208 1.000.97 0.42 0.42 0.10 0.003 0.00 SAPO- — 44 1.00 0.85 0.29 0.29 0.17 0.090.06 34 — 108 1.00 0.88 0.32 0.32 0.15 0.08 0.05 RTH 17 48 1.00 0.670.11 0.11 0.22 0.23 0.10 17 128 1.00 0.82 0.15 0.15 0.21 0.08 0.10 RTH29 48 1.00 0.73 0.10 0.10 0.24 0.17 0.11 29 112 1.00 0.82 0.12 0.12 0.240.07 0.11 ^(a)Butenes include all isomeric butenes (but-1-ene,(Z)-but-2-ene, (E)-but-2-ene and 2-methylpropene ^(b)Selectivity to allfully saturated hydrocarbons containing 1 to 4 carbon atoms^(c)Selectivity to all 5 and 6 carbon species

T Geometrical properties of the three frameworks tested for the MTOreaction are given in Table 7.

TABLE 7 Geometrical Properties of Frameworks Tested for MTOReactions^(a) Channel 8MR opening D_(b) D_(c) Framework system (Å) D_(M)(Å)^(b) D_(a) (Å)^(c) (Å)^(c) (Å)^(c) CHA 3D 3.8 × 3.8 7.37 3.72 3.723.72 LTA 3D 4.1 × 4.1 11.05 4.21 4.2 RTH 3D 3.8 × 3.8 8.18 4.14 1.672.67 2.5 × 5.6 ^(a)All data obtained from the IZA Web site. ^(b)D_(M) isthe maximum included sphere diameter within cages of the material.^(c)D_(a), D_(b), and D_(c) are the maximum free sphere diameters thatcan diffuse along the a, b, and c axes, respectively.

Example 6 Epoxidation Reaction Testing

Allyl alcohol (1.0 mmol), H₂O₂ (1 equivalent, provided using in a 30%solution, and an Ti-LTA catalyst (50 mg) were stirred in 5 mL ofmethanol solvent for 24 hours at 55° C. The solution was thencentrifuged to remove the solid catalyst. The remaining liquid wasrotor-evaporated to remove the solvent, leaving a clear oil, which wasshown to be a mixture of starting material and epoxide by ¹H NMR. Theratio of product epoxide:allyl alcohol was found to be 1:2.

The following references may be useful in understanding certain aspectsof the present disclosure:

-   -   (1) Breck, D. W.; Eversole, W. G.; Milton, R. M.; Reed, T. B.;        Thomas, T. L. J. Am. Chem. Soc. 1956, 78, 5963-5972.    -   (2) Corma, A.; Rey, F.; Rius, J.; Sabater, M. J.; Valencia, S.        Nature 2004, 431 287-290.    -   (3) Huang, A.; Weidenthaler, C.; Caro, J. Microporous Mesoporous        Mater. 2010, 130, 352-356.    -   (4) C. Baerlocher, L. B. Mccusker, “Database of Zeolite        Structures, <http://www.iza-structure.org/databases/>. Accessed        Dec. 8, 2014.,” 2014.    -   (5) B. Yilmaz, U. Müller, Top. Catal. 2009, 52, 888-895.    -   (6) S. I. Zones, Microporous Mesoporous Mater. 2011, 144, 1-8.    -   (7) R. Pophale, F. Daeyaert, M. W. Deem, J. Mater. Chem. A 2013,        1, 6750-6760.    -   (8) M. Moliner, C. Martinez, A. Corma, Chem. Mater. 2014, 26,        246-258.    -   (9) W. Vermeiren, J.-P. Gilson, Top. Catal. 2009, 52, 1131-1161.    -   (10) G. Lewis, M. Miller, J. Moscoso, Stud. Surf. Sci. Catal.        2004, 154, 364-372.    -   (11) J. W. Park, J. Y. Lee, K. S. Kim, S. B. Hong, G. Seo, Appl.        Catal. A Gen. 2008, 339, 36-44.    -   (12) A. Huang, J. Caro, Chem. Commun. (Camb). 2010, 46, 7748-50    -   (13) I. Tiscornia, S. Valencia, A. Corma, C. Téllez, J.        Coronas, J. Santamaria, Microporous Mesoporous Mater. 2008, 110,        303-309.    -   (14) H. K. Hunt, C. M. Lew, M. Sun, Y. Yan, M. E. Davis,        Microporous Mesoporous Mater. 2010, 130, 49-55.    -   (15) M. Sun, H. K. Hunt, C. M. Lew, R. Cai, Y. Liu, Y. Yan,        Chinese J. Catal. 2012, 33, 85-91.    -   (16) B. Harbuzaru, J.-L. Paillaud, J. Patarin, N. Bats, L.        Simon, C. Laroche, U.S. Pat. No. 7,056,490 2006.    -   (17) J. E. Schmidt, S. I. Zones, D. Xie, M. E. Davis,        Microporous Mesoporous Mater. 2014, 200, 132-139.    -   (18) E. J. Fayad, N. Bats, C. E. a Kirschhock, B. Rebours, A.-A.        Quoineaud, J. a Martens, Angew. Chem. Int. Ed. Engl. 2010, 49,        4585-8.    -   (19) S. I. Zones, R. J. Darton, R. Morris, S.-J. Hwang, J. Phys.        Chem. B 2005, 109, 652-61.    -   (20) J. E. Schmidt, M. A. Deimund, M. E. Davis, Chem. Mater.        2014, 26, 7099-7105.    -   (21) Pophale, R.; Daeyaert, F.; Deem, M. W. Computational        Prediction of Chemically Synthesizable Organic Structure        Directing Agents for Zeolites. J. Mater. Chem. A 2013, 1 (23),        6750-6760.    -   (22) Corma, A.; Rey, F.; Rius, J.; Sabater, M. J.; Valencia, S.        Supramolecular Self-Assembled Molecules as Organic Directing        Agent for Synthesis of Zeolites. Nature 2004, 431 (7006),        287-290.    -   (23) J. E. Schmidt and M. E. Davis, WO2014210560

As those skilled in the art will appreciate, numerous modifications andvariations of the present invention are possible in light of theseteachings, and all such are contemplated hereby. For example, inaddition to the embodiments described herein, the present inventioncontemplates and claims those inventions resulting from the combinationof features of the invention cited herein and those of the cited priorart references which complement the features of the present invention.Similarly, it will be appreciated that any described material, feature,or article may be used in combination with any other material, feature,or article, and such combinations are considered within the scope ofthis invention.

All of the references cited in this disclosure are incorporated byreference herein in their entireties for all purposes.

What is claimed:
 1. A process for comprising hydrothermally treating anaqueous composition comprising: (a) a source of a silicon oxide; (b) anoptional source of an aluminum oxide; (c) an optional source of agermanium oxide; (d) an optional source of a titanium oxide; (e) anoptional source of one or more of a boron oxide, gallium oxide, hafniumoxide, iron oxide, tin oxide, indium oxide, vanadium oxide, zinc oxide,zirconium oxide, or combination or mixture thereof; (f) a mineralizingagent; and (g) an organic structure directing agent (OSDA) comprising asubstituted benzyl-3H-imidazol-1-ium cation of Formula (I):

and optionally a tetramethylammonium salt, under conditions effective tocrystallize a crystalline microporous silicate solid of LTA topology;wherein R¹, R², and R⁷ are independently C₁₋₆ alkyl; R³, R⁴, R⁵, R⁶, R⁸,and R⁹ are independently H or C₁₋₃ alkyl; and the substitutedbenzyl-3H-imidazol-1-ium cation has an associated bromide, chloride,fluoride, iodide, nitrate, or hydroxide anion.
 2. The process of claim1, wherein the OSDA comprises a2,3-dialkyl-1-(4-alkyl-benzyl)-3H-imidazol-1-ium cation of Formula (IA):

wherein R¹, R², and R⁷ are independently C₁₋₃ alkyl.
 3. The process ofclaim 1, wherein the OSDA comprises a2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium cation of Formula(IB):

(2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium).
 4. The process ofclaim 1, wherein the aqueous composition comprises: (b) the source ofthe aluminum oxide; (c) the source of the germanium oxide; (d) thesource of the titanium oxide; or (e) a combination of two or more of(b)-(d).
 5. The process of claim 1, wherein the hydrothermal treatmentprovides a crystalline microporous pure-silicate, aluminosilicate,germanosilicate, or titanosilicate solid of LTA topology.
 6. The processof claim 1, wherein: (a) the source of the silicon oxide comprises asilicon alkoxide, a silicate, a silica hydrogel, silicic acid, fumedsilica, colloidal silica, a tetra-alkyl orthosilicate, a silicahydroxide, a silicon alkoxide, or combination thereof; (b) the source ofthe aluminum oxide, when present, comprises an alkoxide, hydroxide, oroxide of aluminum, a sodium aluminate, or combination thereof; (c) thesource of the germanium oxide, when present, comprises a alkali metalorthogermanate, containing discrete GeO₄ ⁴⁻ ions, GeO(OH)₃ ⁻, GeO2(OH)₂²⁻, [(Ge(OH)₄)₈(OH)₃]³⁻ or neutral solutions of germanium dioxidecontaining Ge(OH)₄, or an alkoxide or carboxylate derivative thereof;and (d) the source of the titanium oxide, when present, comprises atitanium alkoxide, oxide, or hydroxy oxide.
 7. The process of claim 1,wherein the mineralizing agent comprises an aqueous alkali metal oralkaline earth metal hydroxide.
 8. The process of claim 1, wherein themineralizing agent comprises hydrofluoric acid (HF).
 9. The process ofclaim 1, wherein the composition has: (a) a molar ratio of the OSDA:Siis in a range of from 0.1 to 1; (b) a molar ratio of Al:Si in a range offrom 0 to 0.1, when the source of the aluminum oxide is present; (c) amolar ratio of Ge:Si in a range of from 0 to 1, when the source of thegermanium oxide is present; (d) a molar ratio of Ti:Si in a range offrom 0 to 0.1, when the source of the titanium oxide is present; (e) amolar ratio of water:Si in a range of from about 2 to about 20; and (f)a molar ratio of fluoride:Si in a range of from about 0.1 to about 0.75,when the mineralizing agent is HF.
 10. The process of claim 9, whereinthe aqueous composition further comprises: (b) the source of thealuminum oxide; (c) the source of the germanium oxide; (d) the source ofthe titanium oxide; or (e) a combination of two or more of (b)-(d). 11.The process of claim 1, wherein the conditions effective to crystallizea crystalline microporous solid of LTA topology include treatment of therespective hydrothermally treated aqueous composition at a temperaturein a range of from 100° C. to 200° C. for a time in a range of from 3 to40 days.
 12. The process of claim 1, further comprising isolating thecrystalline microporous silicate solid of LTA topology.
 13. The processof claim 12, further comprising: (a) heating the isolated crystallinemicroporous solid at a temperature in a range of from about 250° C. toabout 450° C.; (b) contacting the isolated crystalline microporous solidwith ozone or other oxidizing agent at a temperature in a range of 100°C. to 200° C.; or (c) heating the isolated crystalline microporous solidat a temperature in a range of from about 200° C. to about 600° C. inthe presence of an alkali, alkaline earth, transition metal, rare earthmetal, ammonium or alkylammonium salt; for a time sufficient to form adehydrated or an OSDA-depleted product.
 14. The process of claim 13,further comprising: (a) treating the dehydrated or OSDA-depleted productwith an aqueous alkali, alkaline earth, transition metal, rare earthmetal, ammonium or alkylammonium salt; and/or (b) treating thedehydrated or OSDA-depleted product with at least one type of transitionmetal or transition metal oxide.
 15. A crystalline microporous silicatesolid of LTA topology, prepared by the process of claimed 1, containingwithin its pores an OSDA comprising a substitutedbenzyl-3H-imidazol-1-ium cation of Formula (I):

wherein R¹, R², and R⁷ are independently C₁₋₆ alkyl; R³, R⁴, R⁵, R⁶, R⁸,and R⁹ are independently H or C₁₋₃ alkyl.
 16. The crystallinemicroporous silicate solid of LTA topology of claimed 15, wherein thesolid is: (a) a pure-silicate; (b) an aluminosilicate; (c) agermanosilicate; or (d) a titanosilicate.
 17. The crystallinemicroporous silicate solid of LTA topology of claim 15, wherein the OSDAcomprises a 2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium cation ofFormula (IB):


18. A crystalline microporous pure-silicate, aluminosilicate,germanosilicate, or titanosilicate solid of LTA topology preparedaccording to the process of claim
 1. 19. The crystalline microporouspure-silicate, aluminosilicate, germanosilicate, or titanosilicate solidof claim 18, the solid exhibiting a powder XRD pattern having at leastfive characteristic peaks selected from the group consisting of 7.6°±0.3° 2-theta; 10.6° ±0.3° 2-theta; 13.0° ±0.3° 2-theta; 15.1° ±0.3°2-theta; 21.4° ±0.3° 2-theta; 22.7° ±0.3° 2-theta; 25.1° ±0.3° 2-theta;27.3° ±0.3° 2-theta; 28.3° ±0.3° 2-theta; and 31.3° ±0.3° 2-theta. 20.The crystalline microporous pure-silicate, aluminosilicate,germanosilicate, or titanosilicate solid of claim 18, the solidexhibiting a powder XRD pattern having characteristic peaks at 7.6°±0.3° 2-theta; 10.6° ±0.3° 2-theta; 13.0° ±0.3° 2-theta; 22.7 ° ±0.3°2-theta; and 25.1° ±0.3° 2-theta.
 21. The crystalline microporouspure-silicate of claim 18 exhibiting a ²⁹Si Bloch decay NMR spectrumhaving a single resonance at −113.3 ppm, relative to tetramethylsilane,consistent with the silicon being in a single T-site in the LTAstructure.
 22. The crystalline microporous aluminosilicate of claim 18exhibiting an ²⁷Al MAS NMR spectrum consistent with the aluminum beingin a tetrahedral environment.
 23. The crystalline microporous silicatesolid of LTA topology of claim 15, wherein the OSDA comprises a2,3-dialkyl-1-(4-alkyl-benzyl)-3H-imidazol-1-ium cation of Formula (IA):

wherein R¹, R², and R⁷ are independently C₁₋₃ alkyl.
 24. A compositioncomprising: (a) a source of a silicon oxide; (b) an optional source ofan aluminum oxide; (c) an optional source of a germanium oxide; (d) anoptional source of a titanium oxide; (e) an optional source of one ormore of a boron oxide, gallium oxide, hafnium oxide, iron oxide, tinoxide, titanium oxide, indium oxide, vanadium oxide, zinc oxide,zirconium oxide, or combination or mixture thereof; (f) a mineralizingagent; and (g) an organic structure directing agent (OSDA) comprising asubstituted benzyl-3H-imidazol-1-ium cation of Formula (I):

and (h) a compositionally consistent crystalline microporous silicatesolid of LTA topology having the OSDA occluded in its micropores;wherein R¹, R², and R⁷ are independently C₁₋₆ alkyl; R³, R⁴, R⁵, R⁶, R⁸,and R⁹ are independently H or C₁₋₃ alkyl; and the substitutedbenzyl-3H-imidazol-1-ium cation has an associated bromide, chloride,fluoride, iodide, nitrate, or hydroxide anion.
 25. The composition ofclaim 24, wherein the aqueous composition comprises: (b) the source ofthe aluminum oxide and a compositionally consistent crystallinemicroporous aluminosilicate solid of LTA topology; (c) the source of thegermanium oxide and a compositionally consistent crystalline microporousgermanosilicate solid of LTA topology; (d) a source of the titaniumoxide and a compositionally consistent crystalline microporoustitanosilicate solid of LTA topology; or (e) a combination of two ormore of (b)-(d), and wherein: the OSDA comprises a2,3-dimethyl-1-(4-methyl-benzyl)-3H-imidazol-1-ium cation of Formula(IB):


26. The composition of claim 24, wherein the mineralizing agentcomprises hydrofluoric acid (HF).
 27. The composition of claim 24,wherein the composition has: (a) a molar ratio of the OSDA:Si is in arange of from 0.1 to 1; (b) a molar ratio of Al:Si in a range of from 0to 0.1, when the source of the aluminum oxide is present; (c) a molarratio of Ge:Si in a range of from 0 to 1, when the source of thegermanium oxide is present; (d) a molar ratio of Ti:Si in a range offrom 0 to 0.1, when the source of the titanium oxide is present; (e) amolar ratio of water:Si in a range of from about 2 to about 20; and (f)a molar ratio of fluoride:Si in a range of from about 0.1 to about 0.75,when the mineralizing agent is HF.
 28. The composition of claim 27,wherein the aqueous composition comprises: (b) the source of thealuminum oxide; (c) the source of the germanium oxide; (d) the source ofthe titanium oxide; or (e) a combination of two or more of (b)-(d). 29.The composition of claim 24, wherein the composition is a suspension ora gel.
 30. The composition of claim 24, comprising: (b) the source ofthe aluminum oxide; (c) the source of the germanium oxide; (d) thesource of the titanium oxide; or (e) a combination of two or more of(b)-(d), and wherein the OSDA comprises a2,3-dialkyl-1-(4-alkyl-benzyl)-3H-imidazol-1-ium cation of Formula (IA):

wherein R¹, R², and R⁷ are independently C₁₋₃ alkyl.